CA1295773C - Organosilicon polymers - Google Patents
Organosilicon polymersInfo
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- CA1295773C CA1295773C CA000545252A CA545252A CA1295773C CA 1295773 C CA1295773 C CA 1295773C CA 000545252 A CA000545252 A CA 000545252A CA 545252 A CA545252 A CA 545252A CA 1295773 C CA1295773 C CA 1295773C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/14—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
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Abstract
ORGANOSILICON POLYMERS
Abstract of the Disclosure Novel thermoset and thermoplastic organosilicon polymers, comprised substantially of alternating polycyclic hydrocarbon residues and cyclic polysiloxane or tetrahedral siloxysilane residues linked through carbon-silicon bonds, and methods for making them, are disclosed.
Abstract of the Disclosure Novel thermoset and thermoplastic organosilicon polymers, comprised substantially of alternating polycyclic hydrocarbon residues and cyclic polysiloxane or tetrahedral siloxysilane residues linked through carbon-silicon bonds, and methods for making them, are disclosed.
Description
~L~4~-3 j J~J
This invention relates to polymers of certain siloxanes and polyunsaturated hydrocarbons and a method for making them.
It has been known for ~uite some time that compounds containing the hydrosilane (i.e., =Si-~) functional group can be reacted with alkenes containiny vinyl (terminal) un-saturation to form alkyl silanes. The simplest example of this reaction is the addition of trichlorosilane to ethylene to form ethyl trichlorosilane. This exothermic reaction is catalyzed by platinum halide compounds and proceeds readily to virtually 1~0~ conversion.
This reaction, known as the "hy~rosilation" or "hydro-silylation" reaction, has been found effective with a large number of vinyl compounds. Likewise, other silanes such as dialkyl silanes, halo-alkyl silanes, and alkoxy silanes have been found to underyo this reaction so long as they possess the requisite =Si-H group.
A number of organosilicon polymers that have been dis-closed in the prior art are actually vinyl addition polymers modified with silicon-containing moieties. Polymerization takes place in some cases via conventional olefin polymeri-zation routes witnout making use of the hydrosilation reac-tion. The silicon containing moiety is then present as a polymer modifier. Exa~les of such polymerizations can be found in, e.g., U.S. 3,125,554; U.S. 3,375,236; U.S.
3,83~3,115; U.S~ 3,920,714; and U.S. 3,929,850.
A few instances have been reported in which polymeriza-tion takes place via reaction between compounds containing a vinyl silane (=Si-CH=CH2) geoup and a hydrosilane (=Si-H) 1;2~5~/73 ~2- 22124-168~
group to form highly crosslinked, hea~-set polymers. Examples of this type of polymer are found in U.S. Patent Nos. 3,197,432, 3,197,433 and 3,438,936. Each of these patents teaches the preparation of polymers from vinyl alkyl cyclotetrasiloxanes and alkyl cyclotetrasiloxanes containing 2 to 4 silanic hydrogen atoms.
It would be desirable to provide a new class o f high molecular weight organosilicon polymers which have excellent physical, thermal and electrical properties and outstanding resistance to water, and that could be used to prepare shaped articles.
~ ccording to one aspect, the invention provides a crosslinked or crosslinkable organosilicon polymer, characterized in that it comprises alternating polycyclic hydrocarbon residues and cyclic polysiloxanes or siloxysilane residues linked through carbon to silicon bonds, said polymer being the reaction product of (a) a cyclic polysiloxane or a tetrahedral siloxysilane containing at least two hydrosilane groups and (b) a polycyclic polyene having at least two non-aromatic carbon-carbon double bonds in its rings, wherein the ratio of carbon-carbon double bonds in the rings of (b) to hydrosilane groups in (a) is in the range of from greater than 0.5:1 up to 1.8:1, and at least one of (a) or (b) has more than two reactive sites.
If thermoset polymers are desired, the ratio of carbon-~2~S~73 carbon doublQ bond~ of tb) to hy~ro~ no group~ ~n ~ i8 ~n the range o~ ~rom about a . 7:1 ~p to about 1.3:1, more pre~erably from about 0.8:1 up to about 1.1:1. The a1ternating rc~idue~
form ~ cro~linked th~rmosQt stru~ture.
. If thermopla~tic polymers are de~ired, the ratio o~
carbon-carbon double bond~ ~n the rings of tb) to hydro~lane qroups in ta) i3 in the range of from greater than 0.5:1 up to ~bout O.~slor in the range of from about 1.3:1 up to 1.8:1.
Also nccording to tha invention, ~ method of prep~ring the organo~ilicon po1ymers according to the invention is charac-terized in that ~ t compri.~e~ reacting, in the presence of a p1atinum-contain~n~ cataly~t, ~a) a cyclic or tetr~hedral poly-siloxene containing ~t least two hydrosilane groups and tb) a po1ycyolic po1yene, the r~tio o~ c~rbon-~rbon double bond~ $n b) to hydro~ilane group~ in the r~ngs of (a~ being in th~ r~nge of ~rom greater than 0.5:1 up to 1.8:1 ~nd at least one of ~ a ) or tbJ having more than two reactive 3ite~, and ~ub~ecting ~nid polymor to hc~t to dr~v~ th~ cro~linking to a m~ximum.
: 20 Any cyclic polysiloxane or tetrahedral siloxysi1~no with two or more hydroqen atoms bound to ~ilioon will ~nter into the reaction. Cyclic po1ysilox~ne~ u.seu1 in forming tll~ pro-ducts o~ ~hi~ Lnv~ntion ha~e thel y~nerAl ~orm~lla s R ,~, R
S i--O = ~ --~ I ) '~ ~ tO-Si )n ~ ~
R R
- 3a - 22124-16~
wherein R is hydrogen, a saturated, substituted or unsubstituted alkyl or alkoxy radical, a substitu-ted or unsubstituted aromatic or aryloxy radical, n is an integer from 3 to about 20, and R is hydrogen on at least two of the silicon atoms in the molecule.
The tetrahedral siloxysilanes are represented by the general structural formula Si t O-Si-R t ( II) ¦ R
_ _ 4 wherein R is as defined above and is hydrogen on at least two of the silicon atoms in the molecule.
Examples of reactants of Formula (I) include, e.g., .,~ .
;7~
trimethyl cyclotrisiloxane, tetramethyl cyclotetrasiloxane, pentamethyl cyclopentasiloxane, hexamethyl cyclohexasiloxane, tetraethyl cyclotetrasiloxane, cyclotetrasiloxane, tetraphenyl cyclotetrasiloxane, tetraoctyl cyclotetrasiloxane and hexa-methyl tetracyclosiloxane.
The most commonly occurring members of this group are the tetra-, penta-, and hexacyclosiloxanes, with tetramethyl tetracyclosiloxane being a preferred member. In most cases, however, the material is a mixture of a number of species wherein n can vary widely. Generally, commercial mixtures contain up to about 20~ (in purer forms as low as 2%) lo~
molecular weight linear methylhydrosiloxanes, such as hepta-methyltrisiloxane, octamethyltrisiloxane, etc.
Examples of reactants of Formula (II) include, e.g., tetrakisdimethylsiloxysilane, tetrakisdiphenylsiloxysilane, and tetrakisdiethylsiloxysilane. The tetrakisdimethylsiloxy-silane is the best known and preferred species in this group.
Cyclic polyenes which can be employed are polycyclic hydro-carbon compounds having at least two non-aromatic carbon-carbon double bonds in their rings. Exemplary compounds include dicyclopentadiene, methyl dicyclopentadiene, cyclo-pentadiene oligomers, norbornadiene, norbornadiene dimer, hexahydronaphthalene, dimethanohexahydronaphthalene, and substituted derivatives of any of these.
The reaction proceeds readily in the presence of a platinum-containing catalyst. Metal salts and complexes of Group VIII elements can also be used. The preferred catalyst, in terms of both reactivity and cost, is chloroplatinic acid (H2PtC16 6H2O). Catalyst concentrations of 0.0005 to about 0.5~ by weiyht, based on weight of the monomer, will effect smooth and substantially complete polymerization.
Other platinum compounds can also be used to advantage in some instances, such as PtC12 and dibenzonitrile platinum dichloride. Platinurn on carbon is also effective for carrying out high temperature polymerizations. Other useful platinum catalysts are disclosed in, e.g., U.S. Patent Nos. 3,220,972, 3,715,334 and 3,159,662. An exhaustive discussion of the 7'73 catalysis o~ hydrosilation can be found in Advances in Organo-metallic Chemistry, Vol. 17, beginning on page 407. The poly-merization reactions can be promoted thermally or by the addi-tion of radical generators such as peroxides and azo com-pounds.
It will be apparent to the artisan that the polymers of this 1nvention can be homopolymers, i.e., reaction produc~s of one hydrosilane-containing reactant and one polycyclic poly-ene, or they can be interpolymers prepared from a plurality of hydsosilane-containing reactants with one or more poly-cyclic polyene,s. Any combination of silane-containing compound and polycyclic polyene is possible so long as th~ specified ratio of >C=C~ groups to =Si-H groups is met.
one example of a crosslinked, thermoset polymer according to the invention is the reaction product of one mole of tetrakis dimethyl siloxysilane and 2 moles of norbornadiene which when fully cured, has the idealized general structural formula, for the 2,5 isomer (the 2,6 isomer can also be present):
~, o c~ I cn~ CA~ I c~ c 9 ¦ CN~
~~ ~ --~ ~--5~ ~ $----51~0--5~$--O s~--o--s~ ~_ ~ O ch~ c~ I
c~ e~ c~$1~c;~ ;sr~
C?l;~-c~ a~rCI 5 C~
c,~ Q c~, c~, ~ C~3 C~ ~ C~
0~ 0--5~Sl----S~--O--S-~5~--0~ O--S---C'tl~ I C)~ Cll~ I C~ C~ C'l-~
CH-~51-CN~ ClljS~-CI~ C ~S~-Cli~
cn-~Srcl~ C~ -C~ Cl ;S~-c1-3 O O O
-- 51 O Sl--O--51~ 51 O--51--O--Sl ~51--O --Sl --O --Sl O
c ~SI-CH~ Chjsl~cl`l P j ~ C' 3~i~773 It is possible, by selection of reactants, reactant concentrations and reaction conditions, to prepare polymers within the scope of this invention exhibiting a broad range of properties and physical forms. Thus, it has been found S possible to prepare tacky solids, elastomeric materials, and tough glassy polymers.
The unique thermoset polymers of this invention have a range of utilities, depending upon their physical form. Tacky solids are useful as tackifiers in pressure sensitive adhe-sives and as contact adhesives. They are also useful asstructural adhesives, curable in situ, to form strong bonds due to a high affinity of hydrosilane derived silanol groups for polar metal surfaces, especially oxidized metal surfaces.
The elastomeric embodiments make excellent potting compounds for electronic applications since they can be cured in situ and are insensitive to water.
Thermal properties of these thermoset polymers a~e also outstanding. The glass transition temperature (Tg) of a fully cured thermoset polymer is about 200C or higher. Thermal stability is exceilent with usually less than 10~ weight loss at 500C during thermogravimetric analysis. At 1100C in air, they leave about 50% residue. The thermoset polymers are fire resistant and burn very slowly when subjec-ted to a flame.
A particularly striking property of these thermoset poly-mers is their virtually total insensitivity to water. Theyhave been found to be unaffected by boiling water after ex-tended periods.
The thermoset polymers are also resistant to oxidation and to ultraviolet radiation at ordinary temperatures. Above 200C, oxidative crosslinking of silicon portions of the mole-cule appears to take place, resulting in the for~ation of a dark siliceous outer layer. This oxidized outer layer appears to impede the oxidative degradation of the polymer.
The tough, glassy thermoset polymers may be useful in many applications where glass is now employed as, eOg., water heater tank liners. The insensitivity of these thermose~
polymers to water and their high temperature properties make .5773 them ideal for applications of this type. Moreover, the im-pact resistanGe of glass fiber-filled polymer, although not extraordinary, is better than that of slass so that lined tanks can withstand the rigors of shipment, handling and in-stallation better than glass.
The tough glassy thermoset polymers pyrolyze upon heat-ing to greater than 1000C. This high temperature resistance makes them useful as refractory materials, fire resistant materials and ablative materials.
The thermoplastic polymers of this invention generally exhibit melting points in the range of from about 60C to about 130C. However, when post-cured at temperatures greater than 200C, some (for instance, those having a ~C=C<:=Si-H
equivalents ratio of 1.45:1.0) exhibit elastomeric character-istics, and, in some instances, they have higher softening points or exhibit thermoset properties after post-cure.
The thermoplastic polymers of this invention range from tacky to hard, non-tacky solids which have low melting points.
Some of the polymers (e.g., those having a >C=C<:=Si-H equiva-lents ratio of 1.45:1Ø) exhibit thermoplastic behavior (meltflow) until they are heated to a higher temperature (200 to 300C) where they become thermoset polymers. These can be considered thermoplastic-thermoset polymers. These materials can be coated on substrates as powders, melts, or solutions ~5 and cured to give glass transitions somewhat lower than the polymers that have mainly thermoset behavior (e.g., those hav-ing ~C=C<:=Si-H equivalents ratio of about 0.7:1 to about 1.3:1).
To prepare the novel thermoset polymers of this inven-tion, several approaches are available. In the first ap-proach, the correct relative ratios of reactants and the plat-inum catalyst are simply mixed and brought to a temperature at which the reaction is initiated and proper temperature condi-tions are thereafter maintained to drive the reaction to sub-stantial completion (typically, with a >C=C<:=Si-H equivalents ratio of about 1:1, where 70 to 80% of the hydrosilane groups are consumed)0 ~ormally, period~ic temperature increases are desirable to drive the reaction as the molecular weight of the polymer increases. The reaction is normally carried out in a mold, at least up until the point at which sufficient cross-linking has taken place to fix the polymer in the desired shape. Heat treatment can then be continued to drive the re-action further toward completion after removal from the Mold, if necessary. This relatively simple approach is a workable method in cases where the two double bonds in the diene mole-cule are essentially equivalent in their reactivity so that crosslinking begins soon after initiation of the reaction.
Although a hydrosilation reaction via the carbon-carbon unsaturation of the polycyclic polyene rings and the hydro-silane group is the primary polymerization and crosslinking mechanism, other types of polymerization and crosslinking may also take place as the curing temperature is increased. These may include, e.g., oxidative crosslinking, free radical poly-merization (olefin addition reactions) and condensation of silanols to form siloxane bonds.
The initial product of the reaction at lower tempera-tures is often a flowable, heat-curable liquid prepolymer or oligomer (hereafter "prepolymer") even though the ratio of >C=C< to =Si-H is otherwise suitable for crosslinking. Such liquid prepolymers, analogous to the so-called B-stage resins encountered in other thermoset preparations, can be recovered and subsequently transferred to a mold for curing. These vis-cous, flowable liquid prepolymers are stable at room tempera-ture for varying periods of time, but, upon reheating to an appropriate temperature, they cure to the same types of thermoset polymers as are prepared when polymerization is carried out substantially immediately.
The B-stage type prepolymers can be prepared by cooling the reaction mass, following the initial exotherm, to about 30 to 65C and maintaining it at that point for several hours, and then interrupting the reaction by removing the heat until such time as it is desired to complete the transition to a glassy, crosslinked thermoset polymer. The viscous, flowable liquids will be about 30 to 50~ reacted and the viscosity can vary accordingly. By monitoring the viscosity build-up, the practitioner can select, for his own purposes, the point at which the polymerization is to be interrupted.
The thermoplastic polymers can be prepared in substan-tially the same manner as the thermoset polymers. That is,they may simply be prepared by mixing the correct ratios of reactants and catalyst and brouclht to the temperature at which the reaction is initiated. Thereafter, proper temperature conditions can be used to drive the reaction to completion.
It is preLerred for the temperat:ure to be increased periodi-cally as the molecular weight of the polymer increases.
The initial product of the reaction i5 a viscous, flow-able liquid, which may be heated to complete polymerization, as described above. However, since the resultant polymers are thermoplastic, there is generally no need to retain the reactants in the form of a B stage prepolymer or oligomer such as those described above, as the polymer can be heated, molded and cooled to form a shaped article. Such thermoplastic poly-mers can be ground and shipped to a molder where they will be heated and formed into a shaped article. Thus, while liquid prepolymers, oligomers or polymer intermediates can be formed as described above, in most instances it will be preferable to prepare these thermoplastic polymers in the form of a solid, e.g., a powder, ready for use in a molding operation.
A number of options exist for incorporating additives into the polymer. Additives such as fillers and pigments are readily incorporated. Carbon black, vermiculite, mica, wollastonite, calcium carbonate, sand, glass spheres, glass beads, ground glass and waste glass are examples of f illers which can be incorporated. Fillers can serve either as rein-forcement or as fillers and extenders to reduce the cost of the molded product. Glass spheres are useful for preparing low density composites. When used, fillers can be present in amounts up to about 80%. Stabilizers and antioxidants are useful to maintain storage stability of B stage materials and thermal oxidative stability of the final product.
Glass or carbon, e.g., graphite, fibers are wetted very well by the liquid prepolymer embodiment making the polymers excellent matrix materials for high strength composite struc~
tures. Thus a mold containing the requisite staple or con-tinuous filament can be charged with the prepolymer and theprepolymer cured to form the desired composite structure.
Fiber in fa~ric form can also be employed, In addition, solid thermoplastic polymers may be melted, poured over such fibers, and heated to form composites or thermoplastic polymer powders may be blended with such fibers and, then, heated to form a composite. Fiber reinforced composites of the polymers of this invention can contain as much as 80~, preferably 30 to 60%, by weight, of fibrous reinforcement, and, when fully cured, typically exhibit extremely high tensile and flexural properties and also excellent impact strength. other types of fibers, e.g., metallic, ceramic and synthetic polymer fibers, also work well.
The glass filled, thermoset products which have been polymerized to the tough glassy state are characterized by high physical properties, i.e., high modulus and high tensile strength and good flex properties. They are fire resistant, burn very slowly when subjected to a flame, and self-extinguish when the flame is removed.
The following examples are presented to demonstrate this invention. They are not intended to be limiting.
Example 1 This example shows preparation of a novel thermoset poly-mer per this invention by reacting dicyclopentadiene and tetrakisdimethylsiloxysilane, with a ratio of carbon-carbon double bonds to hydrosilane groups of 1:1. -A reaction vessel was dried using an N2 flow and a heatgun (300C pot temperature), stoppered and placed in a nitro-gen flushed glove bag while hot. After equilibratiny, the re-action vessel was tared on a balance, returned to the glove bag, and 0.027 g of Pt C12 was charged. A "dry" 1/2" mag-netic stirrer was charged and the reaction vessel was capped ~$~7~3 ~icyclopentadiene (2.68 g; 0~02 mole) was cnarged to the re-action vessel using a 5 cc syringe. This mixture was heated at 90C for 2 hours with stirring under slow N2 purge to allow the catalyst complex to form. The sample was cooled to 35C, tetrakisdimethylsiloxysilc~ne (3.28 g, 0.01 mole) was charged via syringe and the reaction mixture was returned to the 90C oil bath. After stirring for about 2 minutes, ~he sample foamed and darkened. The sample was further heated in the oil bath to 165C for 3 hours during which time polymer-ization occurred as the sample continued to thicken. Addi-tional heat treatments of 190C for 1/2 hourt and 215 to 235C
for 3 hours were performed. The sample was allowed to cool and removed from the reaction vessel. The final sample was dark, rubbery and tough.
Example 2 This exam~le shows preparation of a film comprising a novel thermoset polymer per this invention, i.e., the reac-tion product of tetramethylcyclotetrasiloxane and norborna-diene, with a ratio of carbon-carbon double bonds to hydro-silane groups of 1:1.
Chloroplatinic acid (0.0030 g, 200 ppm) was charged to areaction vessel under a nitrogen sweep. The reaction vessel was capped and 8.57 g (0.035 mole) tetramethylcyclotetra-siloxane and 6.43 g (0.070 mole) norbornadiene were charged to the sealed reaction vessel by syringe. The reaction vessel contents were blanketed under nitrogen and stirred while heating at 50C for 2.5 hoursO After two hours the initial yellow color disappeared and the viscosity of the fluid increased. After the 2.5 hours at 50C the reaction mixture was diluted by injecting 15 ml dry xylene and filtered through #41 paper to remove insoluble black catalyst residues.
The resulting polymer contained 10 to 50 ppm Pt (x-ray analy-sis).
Films of the filtered toluene solution fifteen mils thick were cast on glass plates with a doctor blade and the xylene was allowed to evaporate overnight. The films on the glass were heated at 100C for 70 hours under nitrogen and then at 200C for 4 hours. The films were immersed in water for a few hours at room temperature and they released from the glass. A visible/uv analysis showed no significant absorbance for these films from 220 to 800 nm.
~ le 3 This example shows preparat:ion of a molded, glass cloth reinforced, article comprising a novel thermoset polymer per this invention by preparing a B stage prepolymer by partially reacting dicyclopentadiene and tetramethylcyclotetrasiloxane (ratio of carbon-carbon double bonds to hydrosilane groups of 1:1), injecting the B stage prepolymer into a mold, and heat-ing to complete polymerization.
Chloroplatinic acid (0.0101 9) was charged to a dry 750 ml reaction vessel in a N2 filled glove bag and the reac-tion vessel was sealed. Dry dicyclopentadiene (26.44 9, 0.2 mole) was charged by syringe. This mixture was heated at 55C
for one hour to form a dicyclopentadiene/H2PtC16 6H20 catalyst complex. Dry tetramethylcyclotetrasiloxane (24.05 g, 0.10 mole) was added gradually at 56C and an immediate exotherm took the temperature to 174C. The mixture was cooled to 64 to 65C and held there for 1.5 hour. Si NMR
shows that the hydrosilation reaction is about 50~ complete at this time. The low viscosity product was removed from the reaction vessel by syringe and injected into a teflon~coated mold containing glass cloth which exactly filled the mold cavity. The resin in the mold was degassed at 60C under a slight vacuum in a vacuum oven. The aspirator vacuum was manually controlled to keep the resin from foaming out of the mold. The mold was heated in an oven at 68C for 18 hours and then at 140 to 150C for 3 days. The oven was cooled slowly and the mold unclamped to give a very hard, stiff 5" x 5" x 1/8" plaque. Samples were cut for rheological, tensile, and flexural property determinations and the following data were obtained:
,~C ~ ~ p 60~ Glass Cloth, 40% TetramethylCyclotetrasiloxane/
Dicvclo~entadiene 1/2 Tensile Strength 23,800 psi 5 Tensile Modulus 1.2 x 106 psi % ~longation (break) 2.2 Flexural Strength 40,400 psi Flexural Modulus 2.2 x 106 psi Rockwell R Hardness 119 10 Glass Transition Temp (Rheometrics) 160C
Notched Izod Impact. 10 ft lb/in notch Heat Distortion Temperature (264 psi) ~300C
Example 4 This example shows preparation of a novel thermoset poly-mer per this invention by reacting norbornadiene and tetra-rmethylcyclotetrasiloxane with a ratio of carbon-carbon double bonds to hydrosilane groups of approximately 1:1.
A dry, N2 sparged vessel was charged with a stir bar and 0.0021 g of H2PtC16-6H20. The vessel was capped and charged with 4.47 g (0.05 mole) of norbornadiene. The result-ing mixture was stirred for thirty minutes at 60C. Tetra-methylcyclotetrasiloxane (5.83 g, 0.024 mole) was added and the reaction mixture gelled about three hours later. The sample was removed from the reaction vessel and cured at 150C
for 16 hours, 250C for 2 hours and 280C for 16 hours to give a brown, glassy solid.
Example 5 This example show preparation of a novel thermoset poly-mer per this invention by reacting dicyclopentadiene and methylcyclotetrasiloxane, with a ratio of carbon-carbon double bonds to hydrosilane groups of approximately 1:1.
Following the general procedure in Example 4, tetra-methylcyclotetrasiloxane (18.1 g, 0.075 mole) was added to a heated (60C) mixture of dicyclopentadiene (20.12 ~, 0.152 mole) and H2PtC16 6H20 (0.0076 g). The reaction mix-ture exothermed to 186C 30 seconds after the tetramethyl-cyclotetrasiloxane addition. The reaction mixture was stirred for 16 hours at 60C, 24 hours at 70C and 5 hours at 150C.
The mixture was poured into an aluminum pan and cured for 12 hours at 200C, 2 hours a~ 225C, 2 hours at 250C and 16 hours at 280C to give a brown glassy solid.
The thermal stability of the polymers of Examples 4 and 5 are presented in the following table.
5TGA (20C/Min.) Example 10~ Wt. Loss~ Residue No. ~ (C~ (1100C) 10Example 6 This example show preparation of a novel molded, thermo-set polymer per this invention by reacting dicyclopentadiene and methylcyclotetramethylsiloxane, with a ratio of carbon-carbon double bonds to hydrosilane groups of approximately 1:1.
Following the general procedure in Example 4, tetra-; methylcyclotetrasiloxane (49.76 g, 0.20 mole) was added to a heated (70C) mixture of dicyclopentadiene (54.71 g, 0.414 mole) and H2PtCl~ 6H20 (0.0209 g). Thirty seconds after the tetramethylcyclotetrasiloxane addition, the reac-tion mixture exothermed to 170C. The reaction mixture was stirred for 16 hours at 130C and poured into a teflon coated mold. The sample was cured for 16 hours at 150C to give an opaque, glassy solid.
Example 7 This example show preparation of a molded, glass cloth reinforced, article comprising a novel thermoset polymer per this invention. A B stage prepolymer was prepared by parti-ally reacting dicyclopentadiene and tetramethyl cyclotetra-~ 30 siloxane in amounts such that the ratio of carbon-carbon ; double bonds to hydrosilane groups was 1.1:1. Then, the B
stage prepolymer was poured into a mold containing a glass cloth and was heated to complete polymerization.
Followinq the general procedure in Example 4, tetra-methylcyclotetrasiloxane (28.6 g, 0.12 mole) was added to a .
heated (55~C) mixture of dicyclopentadiene (34.4 g, 0.26mole) and H2PtC16-6H2O (0.0126 9). Thirty seconds after the tetramethyl cyclotetrasiloxane addition, the reac-tion mixture exothermed t.o }84C. The reaction mixture was stirred for 2 hours at 80C then transferred to a te1On-coated mold containing 50.9 g woven glass cloth. The sample was cured for 12 hours at 130C, for eight hours at 160C, and for 16 hours at 180C to give an opaque, glassy plaque con-taining 60.7 wt. % glass cloth. This plaque was furthe~ cured in a N2 flushed oven at 200C, 250C and 310C for 4 hours at each temperature.
Example 8 This exampie show preparation of a molded, opaque solid plaques comprising a novel thermoset polymer per this inven~
tion, by preparing a B stage prepolymer by partially reacting dicyclopentadiene and tetramethyl cyclotetrasiloxane ,(ratio of carbon-carbon double bonds to hydrosilane groups of 1:1), transferring the B stage prepolymer into a mold, and heating to complete polymerization.
Following the general procedure in ~xample 4, tetra-methylcyclotetrasiloxane (76.36 9, 0.32 mole) was added to a heated (30C) mixture of dicyclopentadiene (83.9 g, 0.64 mole) and H2PtC16~6H2o (0.0148 g). Five minutes after this addition the reaction mixture exothermed to 193~C. The 25 reaction mixture was stirred for 1 hour at 55 to 70C, trans-ferred to teflon-coated molds and cured at 145C for 18 hours under slight vacuum. The opaque solid plaques were further cured to 285C in a N2 flushed oven.
The polymers of Examples 7 and 8 were further subjected to mechanical analysis to determine their glass transition temperature (Tg) and storage modulus (G') at various tempera-tures. Results are recorded in the following table.
~LZ,~73 Mechanical Analysis Wt. ~ TgG' (GPa) at T (C) Example(l) Glass (C)25 100 1~0 180 200 7(a) 60.7 2752.7 2.2 2.0 1,8 1.6 5(b) 60.7 3002.5 2.1 1.8 1.5 1.~
8(a) 0 2450.8 0.57 0.50 0.~3 0.35 (b) 0 2500.78 0.60 0.50 0.40 0.35 (1) a Deno~es data before water boil.
b Denotes data after 5 day water boil.
The data in this table demonstrate the relative water insensitivity of the organosilicon polymers of this inven-tion. The weight gained after 5 days in boiling water was about 0.1~.
Example 9 This example shows preparation of a novel thermoset polymer per this invention by reacting a dicyclopentadiene-oligomer ~omprising about 58.43% dicyclopentadiene, 43.75~
tricyclopentadiene and 5.05% tetracyclopentadiene (analyzed by G.C.), and tetramethylcyclotetrasiloxane (ratio of carbon-carbon double bonds to hydrosilane groups of 0.86:1).
A complex of 0.0076 g Of H2PtC16 6H20 and 21.71 g (0.12 mole) of the dicyclopentadiene oligomer was prepared by heating the two materials under a dry nitrogen blanket for one hour at 50C. Tetramethylcyclotetrasiloxane (16.10 g, 0.07 mole) was added to the yellow complex (complex temperature was 71C). The reaction exothermed to 153C in 8 seconds. The yellow solution was cooled to 30C, poured into Teflon coated slotted molds and cured at 150C/16 hours and 200C/~ hours.
The 112" x 3" x 1/8" test pieces were removed from the mold and post cured at 100C/0.5 hoursl 150C/0.5 hours, 200C/2 hours, 225C/2 hours, 250C/2 hours and 280/16 hours.
The final polymer was a hard glassy solid with a glass transition temperature of 250C and the weight loss by thermogravimetric analysis started at 500C.
.~.Z,~13~7~3 Example 10 This example shows the preparation of a molded article comprising a novel thermoset polymer per this invention, by partially reacting dicyclopentadiene ancl tetramethylcyclo-tetrasiloxane (ratio o~ carbon-carbon double bonds to hydro-silane groups of 1:1) to form a ~ stage type prepolymer, injecting the B stage prepolymer into a mold, and heating to complete polymerization.
The catalyst H2PtC16~6H20 (0.0148 g) was charged to a dried 25 oz. reaction vessel and sealed. Under a ni~ro~
gen blanket 83.95 g (0.635 mole) dicyclopentadiene was charged by syringe. The catalyst and dicyclopentadiene were heated for 90 minutes at 60 to 70C giving a yellow solution which was cooled to 30C. Tetrameth~lcyclotetrasiloxane (76.36 g, 0.317 mole) was added and an exothermic reaction started in two minutes, eventually reaching 193C. After cooling to 55C, a s~mple was injected into a 5" x 5" x 1/8" teflon lined aluminum mold. The polymer was polymerized at temper-atures ranging from 120 to 280C under a blanket of nitrogen.
Some electrical properties of the cured polymer are given below:
Dielectric Constant 2.87 60 Hz 2.83 1 MHz Dissipation 0.0001 60 Hz 25 Factor 0.0002 100 KHz Volume Resistivity ohm-cm 1.6 x 1ol8 Dielectric 381 Strength v/mil A sample of the Example 10 polymer was immersed in boil-ing water for five days. The sample weight increased 0.1%.
The dimensions of the sample (6.75, 1.30 cm, 0.32 cm) were unchanged after the boiling water treatment. The modulus/
temperature curve and glass transition temperature (250C) were also unchanged by the boiling water treatment.
Example_ll This example shows preparation of a novel thermoset poly-mer per this invention by reacting dicyclopentadiene and a mixture of methylhydrocyclosiloxanes, with a ratio o~ carbon-carbon double bonds to hydrosilane groups of 0,7:1.
Chloroplatinic acid (0.0035g) was weighed into an 8 oz.
reaction vessel under a nitrogen blanket in a dry box and the septum was sealed. Dry dicyclopentadiene (8.08g) was injected into the reaction vesse~ by a hypodermic syringe. The con-tents of the reaction vessel were heated to 60 to 65C for 1hour, under a nitrogen blanket, and the chloroplatinic acid dissolved. Dry air was swept through the reaction vessel for lo to 15 minutes and the contents were cooled to 31C.
Methylhydrocyclosiloxanes, consisting of 54% tetramethyl cyclotetrasiloxane, 20~ pentamethyl cyclopentasiloxane, 5%
hexamethyl cyclohexasiloxane, 19% higher methylhydrocyclo-siloxanes (up to approximately ((CH3(H)SiO-)20), and 2%
linear methylhydrosiloxanes, (total 11.93g) were injected and the reaction exothermed to 179C. After cooling the reaction product to 60C, it was poured into a teflon coated stainless steel mold. The mold was placed into a vacuum oven and a vacuum applied (approximately 15 mm Hg pressure, vacuum pump) for 10 to 15 minutes. Then, the mold was heated under nitro-gen for 6 hours at 180C, for 6 hours at 225C, for 2 hours at 235C, and for 4 hours at 285C.
The polymer of this example exhibits thermoset behavior when polymerized at 225C. The polymer does not have a melt-ing point, but softens at 100C to a soft extendable elasto-; mer. The polymer is a tough, leathe~ like solid at room temperature. It is flexible enough to be twisted 360 beforetearing.
Example 1~
This example shows preparation of a novel thermoset poly-mer per this invention by reacting dicyclopentadiene and methylhydrocyclosiloxanes in the same manner as in example 11, except that the monomers were used in amounts such that the . . --19--ratio of carbon-carbon double bonds to hydrosilane groups was 0.85:1 and the final heating was for 15 hours at 130C, for 6 hours at 160C, for 16 hours at 180C, for 4 hours at 200C, and for 4 hours at 225C.
The thermoset polymer formed after heating to 225C was tougher than that from example 11~ This hard, solid polymer maintains a high modulus up to 200C and exhibits elastomeric behavior when heated to 235C.
Exampl _ ThiS example shows preparation of a novel thermoset poly mer per this invention by reacting dicyclopentadiene and methylhydrocyclosiloxanes in the same manner as in example 11, except that the monomers were used in amounts such that -the ratio of carbon-carbon double bonds to hydrosilane groups of 1.15:1 and the final heating was for 4 hours at 150C, for 2 hours at 235C, and for 4 hours at 285C.
Example 14 This example shows preparation of a novel thermoset poly-mer per this invention by reacting dicyclopentadiene and methylhydrocyclosiloxanes in the same manner as in example ; 13, except that the monomers were used in amounts such that the ratio of carbon-carbon double bonds to hydrosilane groups of 1.30:1.
All the polymers produced in examples 12 to 14 exhibited thermoset characteristics and did not melt or lose their shape at temperatures below the decomposition points of the polymers (400 to 500C). Polymers prepared from reactants having a carbon-carbon double bond:hydrosilane equivalents ratio near 1:1 were post-cured at 285 to 300C to increase their glass transition temperature to the 260 to 300C range. The cross-link density of such polymers was high enough to prevent seg-mental motion and network deformation.
~Z~7~
Example 15 This example shows preparation of a novel thermoset poly-mer per this invention by reacting dicyclopentadiene and methylhydrocyclosiloxanes in the same manner as in example 11, except that the monomers were used in amounts such that the ratio of carbon-carbon double bonds to hydrosilane groups was 1.46:1 and the final heating was for 6 hours at 150C, for 6 hours at 200C, Eor 2 hours at 235C, and for 4 hours at 285C.
Example 15 demonstrates polymerization in the transition range from thermoset behavior to thermoplastic behavior. When polymerized up to 200C, the sample so~tened to a highly com pressible elastomer at about 120 to 125C. When the sample was post-cured at 285C, the glass transition temperature was raised to only 200C. The degree of crosslinking was limited by available hydrosilane yroups.
ExamE~e 16 This example shows preparation of a novel thermoplastic polymer per this invention by reacting dicyclopentadiene and methylhydrocyclosiloxanes in the same manner as in example 11, except in amounts such that the ratio of carbon-carbon double bonds to hydrosilane groups was 1.61:1 and the final heating was for 6 hours at 150C, for 6 hours at 2003C, for 8 hours at 235C, and for 4 hours at 285C.
Exam~le 17 This example shows preparation of a novel thermoplastic polymer per this invention by reactlng dicyclopentadiene and methylhydrocyclosiloxanes in amounts such that the ratio of carbon-carbon double bonds to hydrosilane groups was 1.75:1.
A catalyst solution containiny 600 ~pm chloroplatinic acid was prepared by heating 0.0953g of chloroplatinic acid with 158.8g dicyclopentadiene to 70C for 1.5 hours in a sealed 8 ounce reaction vessel, under nitrogen. A 150 ppm chloroplatinic acid solution was prepared by diluting 30g of 7~
the above catalyst solution with 90g of dicyclopentadiene. A
portion of the resultant chloroplatinic acid solution (7.92g) was weighed into a 7 inch reaction vessel with 4.59g of dicy-clopentadiene, making a 95 ppm concentration of chloroplatinic acid in dicyclopenta~iene (0.185 gram equivalent of olefin~.
Then, 7.21 g (0.106 hydrosilane equivalents) of methyl-siloxanes (described in example 11) were injected into the sealed reaction vessel at 23C. The reaction mixture was - heated to 36C and a slight exotherm raised the temperature to 60C, where the mixture became viscous. A vacuum (15 mm Hg) was applied to the contents of the reaction vessel at 45C for 10 minutes to pull gas out of the reaction product. The product was poured into a teflon coated stainless steel mold and heated in a nitrogen blanket for 6 hours at 150C, for 20 hours at 200C, and for 6 hours at 225 to 235~C. The 3" x 1/2" x 1/8" specimens removed from the mold were transparent, hard solid with a melting point of 117 to 125C. This solid could be ground into a crystalline powder.
The polymers of examples 16 and 17 do not form a com-plete polymeric network, even when they are polymerized at 225 to 235C. They are completely thermoplastic and form a viscous, flowable liquid above their melting points. The solids can be ground into powder.
The properties of the polymers prepared in examples 11 to 17 are shown in the following Table.
-22~ 73 .
r~ "~ O ~
~ ~ .
nl~
~I r~ a~ o u u O ~ ~ O _~
A . O
r~ rl n ,~
! ~ ~ ,. ~ o u~ o 1~ o o I~ s ~,~ ~ . u ~ ~ ~ u o ~ I o O ,~ o ~ ,n O ~ 1 1 U
¦
r~ O U- 111 Ul O O I I I r ~ UO O Cl-~ o o o ~ o f3~ e ~, ~ ~ 2 ~ h U ~U
& ~ e -In o In ~
Example 18 This example shows preparation of graphite fiber com-posite.
Chloroplatinic acid (0.0185g) was weighed into a reac-tion vessel in a dry box and the reaction vessel was sealed.Dicyclopentadiene (47.15g, 0.357 mole, 0.714 equivalents) was injected into the reaction vessel and the mixture was heated with stirring to 60C for 1 hour. After cooling to 36C, tetramethylcyclotetrasiloxane ~44.67g) was injected. In two minutes, the sample exothermed to 192C. The product was cooled and injected into a teflon lined mold 5" x 5" x 1/8"
containing ten 5" x 5" sheets of square woven graphite fiber cloth. The loaded mold was heated in a nitrogen blanketed oven for 15 hours at 130C, for 6 hours at 160C, and for 12 hours at 180C. The resulting composite had good flexural strength t68,000 psi) and modulus (4.7 x 106 psi).
This invention relates to polymers of certain siloxanes and polyunsaturated hydrocarbons and a method for making them.
It has been known for ~uite some time that compounds containing the hydrosilane (i.e., =Si-~) functional group can be reacted with alkenes containiny vinyl (terminal) un-saturation to form alkyl silanes. The simplest example of this reaction is the addition of trichlorosilane to ethylene to form ethyl trichlorosilane. This exothermic reaction is catalyzed by platinum halide compounds and proceeds readily to virtually 1~0~ conversion.
This reaction, known as the "hy~rosilation" or "hydro-silylation" reaction, has been found effective with a large number of vinyl compounds. Likewise, other silanes such as dialkyl silanes, halo-alkyl silanes, and alkoxy silanes have been found to underyo this reaction so long as they possess the requisite =Si-H group.
A number of organosilicon polymers that have been dis-closed in the prior art are actually vinyl addition polymers modified with silicon-containing moieties. Polymerization takes place in some cases via conventional olefin polymeri-zation routes witnout making use of the hydrosilation reac-tion. The silicon containing moiety is then present as a polymer modifier. Exa~les of such polymerizations can be found in, e.g., U.S. 3,125,554; U.S. 3,375,236; U.S.
3,83~3,115; U.S~ 3,920,714; and U.S. 3,929,850.
A few instances have been reported in which polymeriza-tion takes place via reaction between compounds containing a vinyl silane (=Si-CH=CH2) geoup and a hydrosilane (=Si-H) 1;2~5~/73 ~2- 22124-168~
group to form highly crosslinked, hea~-set polymers. Examples of this type of polymer are found in U.S. Patent Nos. 3,197,432, 3,197,433 and 3,438,936. Each of these patents teaches the preparation of polymers from vinyl alkyl cyclotetrasiloxanes and alkyl cyclotetrasiloxanes containing 2 to 4 silanic hydrogen atoms.
It would be desirable to provide a new class o f high molecular weight organosilicon polymers which have excellent physical, thermal and electrical properties and outstanding resistance to water, and that could be used to prepare shaped articles.
~ ccording to one aspect, the invention provides a crosslinked or crosslinkable organosilicon polymer, characterized in that it comprises alternating polycyclic hydrocarbon residues and cyclic polysiloxanes or siloxysilane residues linked through carbon to silicon bonds, said polymer being the reaction product of (a) a cyclic polysiloxane or a tetrahedral siloxysilane containing at least two hydrosilane groups and (b) a polycyclic polyene having at least two non-aromatic carbon-carbon double bonds in its rings, wherein the ratio of carbon-carbon double bonds in the rings of (b) to hydrosilane groups in (a) is in the range of from greater than 0.5:1 up to 1.8:1, and at least one of (a) or (b) has more than two reactive sites.
If thermoset polymers are desired, the ratio of carbon-~2~S~73 carbon doublQ bond~ of tb) to hy~ro~ no group~ ~n ~ i8 ~n the range o~ ~rom about a . 7:1 ~p to about 1.3:1, more pre~erably from about 0.8:1 up to about 1.1:1. The a1ternating rc~idue~
form ~ cro~linked th~rmosQt stru~ture.
. If thermopla~tic polymers are de~ired, the ratio o~
carbon-carbon double bond~ ~n the rings of tb) to hydro~lane qroups in ta) i3 in the range of from greater than 0.5:1 up to ~bout O.~slor in the range of from about 1.3:1 up to 1.8:1.
Also nccording to tha invention, ~ method of prep~ring the organo~ilicon po1ymers according to the invention is charac-terized in that ~ t compri.~e~ reacting, in the presence of a p1atinum-contain~n~ cataly~t, ~a) a cyclic or tetr~hedral poly-siloxene containing ~t least two hydrosilane groups and tb) a po1ycyolic po1yene, the r~tio o~ c~rbon-~rbon double bond~ $n b) to hydro~ilane group~ in the r~ngs of (a~ being in th~ r~nge of ~rom greater than 0.5:1 up to 1.8:1 ~nd at least one of ~ a ) or tbJ having more than two reactive 3ite~, and ~ub~ecting ~nid polymor to hc~t to dr~v~ th~ cro~linking to a m~ximum.
: 20 Any cyclic polysiloxane or tetrahedral siloxysi1~no with two or more hydroqen atoms bound to ~ilioon will ~nter into the reaction. Cyclic po1ysilox~ne~ u.seu1 in forming tll~ pro-ducts o~ ~hi~ Lnv~ntion ha~e thel y~nerAl ~orm~lla s R ,~, R
S i--O = ~ --~ I ) '~ ~ tO-Si )n ~ ~
R R
- 3a - 22124-16~
wherein R is hydrogen, a saturated, substituted or unsubstituted alkyl or alkoxy radical, a substitu-ted or unsubstituted aromatic or aryloxy radical, n is an integer from 3 to about 20, and R is hydrogen on at least two of the silicon atoms in the molecule.
The tetrahedral siloxysilanes are represented by the general structural formula Si t O-Si-R t ( II) ¦ R
_ _ 4 wherein R is as defined above and is hydrogen on at least two of the silicon atoms in the molecule.
Examples of reactants of Formula (I) include, e.g., .,~ .
;7~
trimethyl cyclotrisiloxane, tetramethyl cyclotetrasiloxane, pentamethyl cyclopentasiloxane, hexamethyl cyclohexasiloxane, tetraethyl cyclotetrasiloxane, cyclotetrasiloxane, tetraphenyl cyclotetrasiloxane, tetraoctyl cyclotetrasiloxane and hexa-methyl tetracyclosiloxane.
The most commonly occurring members of this group are the tetra-, penta-, and hexacyclosiloxanes, with tetramethyl tetracyclosiloxane being a preferred member. In most cases, however, the material is a mixture of a number of species wherein n can vary widely. Generally, commercial mixtures contain up to about 20~ (in purer forms as low as 2%) lo~
molecular weight linear methylhydrosiloxanes, such as hepta-methyltrisiloxane, octamethyltrisiloxane, etc.
Examples of reactants of Formula (II) include, e.g., tetrakisdimethylsiloxysilane, tetrakisdiphenylsiloxysilane, and tetrakisdiethylsiloxysilane. The tetrakisdimethylsiloxy-silane is the best known and preferred species in this group.
Cyclic polyenes which can be employed are polycyclic hydro-carbon compounds having at least two non-aromatic carbon-carbon double bonds in their rings. Exemplary compounds include dicyclopentadiene, methyl dicyclopentadiene, cyclo-pentadiene oligomers, norbornadiene, norbornadiene dimer, hexahydronaphthalene, dimethanohexahydronaphthalene, and substituted derivatives of any of these.
The reaction proceeds readily in the presence of a platinum-containing catalyst. Metal salts and complexes of Group VIII elements can also be used. The preferred catalyst, in terms of both reactivity and cost, is chloroplatinic acid (H2PtC16 6H2O). Catalyst concentrations of 0.0005 to about 0.5~ by weiyht, based on weight of the monomer, will effect smooth and substantially complete polymerization.
Other platinum compounds can also be used to advantage in some instances, such as PtC12 and dibenzonitrile platinum dichloride. Platinurn on carbon is also effective for carrying out high temperature polymerizations. Other useful platinum catalysts are disclosed in, e.g., U.S. Patent Nos. 3,220,972, 3,715,334 and 3,159,662. An exhaustive discussion of the 7'73 catalysis o~ hydrosilation can be found in Advances in Organo-metallic Chemistry, Vol. 17, beginning on page 407. The poly-merization reactions can be promoted thermally or by the addi-tion of radical generators such as peroxides and azo com-pounds.
It will be apparent to the artisan that the polymers of this 1nvention can be homopolymers, i.e., reaction produc~s of one hydrosilane-containing reactant and one polycyclic poly-ene, or they can be interpolymers prepared from a plurality of hydsosilane-containing reactants with one or more poly-cyclic polyene,s. Any combination of silane-containing compound and polycyclic polyene is possible so long as th~ specified ratio of >C=C~ groups to =Si-H groups is met.
one example of a crosslinked, thermoset polymer according to the invention is the reaction product of one mole of tetrakis dimethyl siloxysilane and 2 moles of norbornadiene which when fully cured, has the idealized general structural formula, for the 2,5 isomer (the 2,6 isomer can also be present):
~, o c~ I cn~ CA~ I c~ c 9 ¦ CN~
~~ ~ --~ ~--5~ ~ $----51~0--5~$--O s~--o--s~ ~_ ~ O ch~ c~ I
c~ e~ c~$1~c;~ ;sr~
C?l;~-c~ a~rCI 5 C~
c,~ Q c~, c~, ~ C~3 C~ ~ C~
0~ 0--5~Sl----S~--O--S-~5~--0~ O--S---C'tl~ I C)~ Cll~ I C~ C~ C'l-~
CH-~51-CN~ ClljS~-CI~ C ~S~-Cli~
cn-~Srcl~ C~ -C~ Cl ;S~-c1-3 O O O
-- 51 O Sl--O--51~ 51 O--51--O--Sl ~51--O --Sl --O --Sl O
c ~SI-CH~ Chjsl~cl`l P j ~ C' 3~i~773 It is possible, by selection of reactants, reactant concentrations and reaction conditions, to prepare polymers within the scope of this invention exhibiting a broad range of properties and physical forms. Thus, it has been found S possible to prepare tacky solids, elastomeric materials, and tough glassy polymers.
The unique thermoset polymers of this invention have a range of utilities, depending upon their physical form. Tacky solids are useful as tackifiers in pressure sensitive adhe-sives and as contact adhesives. They are also useful asstructural adhesives, curable in situ, to form strong bonds due to a high affinity of hydrosilane derived silanol groups for polar metal surfaces, especially oxidized metal surfaces.
The elastomeric embodiments make excellent potting compounds for electronic applications since they can be cured in situ and are insensitive to water.
Thermal properties of these thermoset polymers a~e also outstanding. The glass transition temperature (Tg) of a fully cured thermoset polymer is about 200C or higher. Thermal stability is exceilent with usually less than 10~ weight loss at 500C during thermogravimetric analysis. At 1100C in air, they leave about 50% residue. The thermoset polymers are fire resistant and burn very slowly when subjec-ted to a flame.
A particularly striking property of these thermoset poly-mers is their virtually total insensitivity to water. Theyhave been found to be unaffected by boiling water after ex-tended periods.
The thermoset polymers are also resistant to oxidation and to ultraviolet radiation at ordinary temperatures. Above 200C, oxidative crosslinking of silicon portions of the mole-cule appears to take place, resulting in the for~ation of a dark siliceous outer layer. This oxidized outer layer appears to impede the oxidative degradation of the polymer.
The tough, glassy thermoset polymers may be useful in many applications where glass is now employed as, eOg., water heater tank liners. The insensitivity of these thermose~
polymers to water and their high temperature properties make .5773 them ideal for applications of this type. Moreover, the im-pact resistanGe of glass fiber-filled polymer, although not extraordinary, is better than that of slass so that lined tanks can withstand the rigors of shipment, handling and in-stallation better than glass.
The tough glassy thermoset polymers pyrolyze upon heat-ing to greater than 1000C. This high temperature resistance makes them useful as refractory materials, fire resistant materials and ablative materials.
The thermoplastic polymers of this invention generally exhibit melting points in the range of from about 60C to about 130C. However, when post-cured at temperatures greater than 200C, some (for instance, those having a ~C=C<:=Si-H
equivalents ratio of 1.45:1.0) exhibit elastomeric character-istics, and, in some instances, they have higher softening points or exhibit thermoset properties after post-cure.
The thermoplastic polymers of this invention range from tacky to hard, non-tacky solids which have low melting points.
Some of the polymers (e.g., those having a >C=C<:=Si-H equiva-lents ratio of 1.45:1Ø) exhibit thermoplastic behavior (meltflow) until they are heated to a higher temperature (200 to 300C) where they become thermoset polymers. These can be considered thermoplastic-thermoset polymers. These materials can be coated on substrates as powders, melts, or solutions ~5 and cured to give glass transitions somewhat lower than the polymers that have mainly thermoset behavior (e.g., those hav-ing ~C=C<:=Si-H equivalents ratio of about 0.7:1 to about 1.3:1).
To prepare the novel thermoset polymers of this inven-tion, several approaches are available. In the first ap-proach, the correct relative ratios of reactants and the plat-inum catalyst are simply mixed and brought to a temperature at which the reaction is initiated and proper temperature condi-tions are thereafter maintained to drive the reaction to sub-stantial completion (typically, with a >C=C<:=Si-H equivalents ratio of about 1:1, where 70 to 80% of the hydrosilane groups are consumed)0 ~ormally, period~ic temperature increases are desirable to drive the reaction as the molecular weight of the polymer increases. The reaction is normally carried out in a mold, at least up until the point at which sufficient cross-linking has taken place to fix the polymer in the desired shape. Heat treatment can then be continued to drive the re-action further toward completion after removal from the Mold, if necessary. This relatively simple approach is a workable method in cases where the two double bonds in the diene mole-cule are essentially equivalent in their reactivity so that crosslinking begins soon after initiation of the reaction.
Although a hydrosilation reaction via the carbon-carbon unsaturation of the polycyclic polyene rings and the hydro-silane group is the primary polymerization and crosslinking mechanism, other types of polymerization and crosslinking may also take place as the curing temperature is increased. These may include, e.g., oxidative crosslinking, free radical poly-merization (olefin addition reactions) and condensation of silanols to form siloxane bonds.
The initial product of the reaction at lower tempera-tures is often a flowable, heat-curable liquid prepolymer or oligomer (hereafter "prepolymer") even though the ratio of >C=C< to =Si-H is otherwise suitable for crosslinking. Such liquid prepolymers, analogous to the so-called B-stage resins encountered in other thermoset preparations, can be recovered and subsequently transferred to a mold for curing. These vis-cous, flowable liquid prepolymers are stable at room tempera-ture for varying periods of time, but, upon reheating to an appropriate temperature, they cure to the same types of thermoset polymers as are prepared when polymerization is carried out substantially immediately.
The B-stage type prepolymers can be prepared by cooling the reaction mass, following the initial exotherm, to about 30 to 65C and maintaining it at that point for several hours, and then interrupting the reaction by removing the heat until such time as it is desired to complete the transition to a glassy, crosslinked thermoset polymer. The viscous, flowable liquids will be about 30 to 50~ reacted and the viscosity can vary accordingly. By monitoring the viscosity build-up, the practitioner can select, for his own purposes, the point at which the polymerization is to be interrupted.
The thermoplastic polymers can be prepared in substan-tially the same manner as the thermoset polymers. That is,they may simply be prepared by mixing the correct ratios of reactants and catalyst and brouclht to the temperature at which the reaction is initiated. Thereafter, proper temperature conditions can be used to drive the reaction to completion.
It is preLerred for the temperat:ure to be increased periodi-cally as the molecular weight of the polymer increases.
The initial product of the reaction i5 a viscous, flow-able liquid, which may be heated to complete polymerization, as described above. However, since the resultant polymers are thermoplastic, there is generally no need to retain the reactants in the form of a B stage prepolymer or oligomer such as those described above, as the polymer can be heated, molded and cooled to form a shaped article. Such thermoplastic poly-mers can be ground and shipped to a molder where they will be heated and formed into a shaped article. Thus, while liquid prepolymers, oligomers or polymer intermediates can be formed as described above, in most instances it will be preferable to prepare these thermoplastic polymers in the form of a solid, e.g., a powder, ready for use in a molding operation.
A number of options exist for incorporating additives into the polymer. Additives such as fillers and pigments are readily incorporated. Carbon black, vermiculite, mica, wollastonite, calcium carbonate, sand, glass spheres, glass beads, ground glass and waste glass are examples of f illers which can be incorporated. Fillers can serve either as rein-forcement or as fillers and extenders to reduce the cost of the molded product. Glass spheres are useful for preparing low density composites. When used, fillers can be present in amounts up to about 80%. Stabilizers and antioxidants are useful to maintain storage stability of B stage materials and thermal oxidative stability of the final product.
Glass or carbon, e.g., graphite, fibers are wetted very well by the liquid prepolymer embodiment making the polymers excellent matrix materials for high strength composite struc~
tures. Thus a mold containing the requisite staple or con-tinuous filament can be charged with the prepolymer and theprepolymer cured to form the desired composite structure.
Fiber in fa~ric form can also be employed, In addition, solid thermoplastic polymers may be melted, poured over such fibers, and heated to form composites or thermoplastic polymer powders may be blended with such fibers and, then, heated to form a composite. Fiber reinforced composites of the polymers of this invention can contain as much as 80~, preferably 30 to 60%, by weight, of fibrous reinforcement, and, when fully cured, typically exhibit extremely high tensile and flexural properties and also excellent impact strength. other types of fibers, e.g., metallic, ceramic and synthetic polymer fibers, also work well.
The glass filled, thermoset products which have been polymerized to the tough glassy state are characterized by high physical properties, i.e., high modulus and high tensile strength and good flex properties. They are fire resistant, burn very slowly when subjected to a flame, and self-extinguish when the flame is removed.
The following examples are presented to demonstrate this invention. They are not intended to be limiting.
Example 1 This example shows preparation of a novel thermoset poly-mer per this invention by reacting dicyclopentadiene and tetrakisdimethylsiloxysilane, with a ratio of carbon-carbon double bonds to hydrosilane groups of 1:1. -A reaction vessel was dried using an N2 flow and a heatgun (300C pot temperature), stoppered and placed in a nitro-gen flushed glove bag while hot. After equilibratiny, the re-action vessel was tared on a balance, returned to the glove bag, and 0.027 g of Pt C12 was charged. A "dry" 1/2" mag-netic stirrer was charged and the reaction vessel was capped ~$~7~3 ~icyclopentadiene (2.68 g; 0~02 mole) was cnarged to the re-action vessel using a 5 cc syringe. This mixture was heated at 90C for 2 hours with stirring under slow N2 purge to allow the catalyst complex to form. The sample was cooled to 35C, tetrakisdimethylsiloxysilc~ne (3.28 g, 0.01 mole) was charged via syringe and the reaction mixture was returned to the 90C oil bath. After stirring for about 2 minutes, ~he sample foamed and darkened. The sample was further heated in the oil bath to 165C for 3 hours during which time polymer-ization occurred as the sample continued to thicken. Addi-tional heat treatments of 190C for 1/2 hourt and 215 to 235C
for 3 hours were performed. The sample was allowed to cool and removed from the reaction vessel. The final sample was dark, rubbery and tough.
Example 2 This exam~le shows preparation of a film comprising a novel thermoset polymer per this invention, i.e., the reac-tion product of tetramethylcyclotetrasiloxane and norborna-diene, with a ratio of carbon-carbon double bonds to hydro-silane groups of 1:1.
Chloroplatinic acid (0.0030 g, 200 ppm) was charged to areaction vessel under a nitrogen sweep. The reaction vessel was capped and 8.57 g (0.035 mole) tetramethylcyclotetra-siloxane and 6.43 g (0.070 mole) norbornadiene were charged to the sealed reaction vessel by syringe. The reaction vessel contents were blanketed under nitrogen and stirred while heating at 50C for 2.5 hoursO After two hours the initial yellow color disappeared and the viscosity of the fluid increased. After the 2.5 hours at 50C the reaction mixture was diluted by injecting 15 ml dry xylene and filtered through #41 paper to remove insoluble black catalyst residues.
The resulting polymer contained 10 to 50 ppm Pt (x-ray analy-sis).
Films of the filtered toluene solution fifteen mils thick were cast on glass plates with a doctor blade and the xylene was allowed to evaporate overnight. The films on the glass were heated at 100C for 70 hours under nitrogen and then at 200C for 4 hours. The films were immersed in water for a few hours at room temperature and they released from the glass. A visible/uv analysis showed no significant absorbance for these films from 220 to 800 nm.
~ le 3 This example shows preparat:ion of a molded, glass cloth reinforced, article comprising a novel thermoset polymer per this invention by preparing a B stage prepolymer by partially reacting dicyclopentadiene and tetramethylcyclotetrasiloxane (ratio of carbon-carbon double bonds to hydrosilane groups of 1:1), injecting the B stage prepolymer into a mold, and heat-ing to complete polymerization.
Chloroplatinic acid (0.0101 9) was charged to a dry 750 ml reaction vessel in a N2 filled glove bag and the reac-tion vessel was sealed. Dry dicyclopentadiene (26.44 9, 0.2 mole) was charged by syringe. This mixture was heated at 55C
for one hour to form a dicyclopentadiene/H2PtC16 6H20 catalyst complex. Dry tetramethylcyclotetrasiloxane (24.05 g, 0.10 mole) was added gradually at 56C and an immediate exotherm took the temperature to 174C. The mixture was cooled to 64 to 65C and held there for 1.5 hour. Si NMR
shows that the hydrosilation reaction is about 50~ complete at this time. The low viscosity product was removed from the reaction vessel by syringe and injected into a teflon~coated mold containing glass cloth which exactly filled the mold cavity. The resin in the mold was degassed at 60C under a slight vacuum in a vacuum oven. The aspirator vacuum was manually controlled to keep the resin from foaming out of the mold. The mold was heated in an oven at 68C for 18 hours and then at 140 to 150C for 3 days. The oven was cooled slowly and the mold unclamped to give a very hard, stiff 5" x 5" x 1/8" plaque. Samples were cut for rheological, tensile, and flexural property determinations and the following data were obtained:
,~C ~ ~ p 60~ Glass Cloth, 40% TetramethylCyclotetrasiloxane/
Dicvclo~entadiene 1/2 Tensile Strength 23,800 psi 5 Tensile Modulus 1.2 x 106 psi % ~longation (break) 2.2 Flexural Strength 40,400 psi Flexural Modulus 2.2 x 106 psi Rockwell R Hardness 119 10 Glass Transition Temp (Rheometrics) 160C
Notched Izod Impact. 10 ft lb/in notch Heat Distortion Temperature (264 psi) ~300C
Example 4 This example shows preparation of a novel thermoset poly-mer per this invention by reacting norbornadiene and tetra-rmethylcyclotetrasiloxane with a ratio of carbon-carbon double bonds to hydrosilane groups of approximately 1:1.
A dry, N2 sparged vessel was charged with a stir bar and 0.0021 g of H2PtC16-6H20. The vessel was capped and charged with 4.47 g (0.05 mole) of norbornadiene. The result-ing mixture was stirred for thirty minutes at 60C. Tetra-methylcyclotetrasiloxane (5.83 g, 0.024 mole) was added and the reaction mixture gelled about three hours later. The sample was removed from the reaction vessel and cured at 150C
for 16 hours, 250C for 2 hours and 280C for 16 hours to give a brown, glassy solid.
Example 5 This example show preparation of a novel thermoset poly-mer per this invention by reacting dicyclopentadiene and methylcyclotetrasiloxane, with a ratio of carbon-carbon double bonds to hydrosilane groups of approximately 1:1.
Following the general procedure in Example 4, tetra-methylcyclotetrasiloxane (18.1 g, 0.075 mole) was added to a heated (60C) mixture of dicyclopentadiene (20.12 ~, 0.152 mole) and H2PtC16 6H20 (0.0076 g). The reaction mix-ture exothermed to 186C 30 seconds after the tetramethyl-cyclotetrasiloxane addition. The reaction mixture was stirred for 16 hours at 60C, 24 hours at 70C and 5 hours at 150C.
The mixture was poured into an aluminum pan and cured for 12 hours at 200C, 2 hours a~ 225C, 2 hours at 250C and 16 hours at 280C to give a brown glassy solid.
The thermal stability of the polymers of Examples 4 and 5 are presented in the following table.
5TGA (20C/Min.) Example 10~ Wt. Loss~ Residue No. ~ (C~ (1100C) 10Example 6 This example show preparation of a novel molded, thermo-set polymer per this invention by reacting dicyclopentadiene and methylcyclotetramethylsiloxane, with a ratio of carbon-carbon double bonds to hydrosilane groups of approximately 1:1.
Following the general procedure in Example 4, tetra-; methylcyclotetrasiloxane (49.76 g, 0.20 mole) was added to a heated (70C) mixture of dicyclopentadiene (54.71 g, 0.414 mole) and H2PtCl~ 6H20 (0.0209 g). Thirty seconds after the tetramethylcyclotetrasiloxane addition, the reac-tion mixture exothermed to 170C. The reaction mixture was stirred for 16 hours at 130C and poured into a teflon coated mold. The sample was cured for 16 hours at 150C to give an opaque, glassy solid.
Example 7 This example show preparation of a molded, glass cloth reinforced, article comprising a novel thermoset polymer per this invention. A B stage prepolymer was prepared by parti-ally reacting dicyclopentadiene and tetramethyl cyclotetra-~ 30 siloxane in amounts such that the ratio of carbon-carbon ; double bonds to hydrosilane groups was 1.1:1. Then, the B
stage prepolymer was poured into a mold containing a glass cloth and was heated to complete polymerization.
Followinq the general procedure in Example 4, tetra-methylcyclotetrasiloxane (28.6 g, 0.12 mole) was added to a .
heated (55~C) mixture of dicyclopentadiene (34.4 g, 0.26mole) and H2PtC16-6H2O (0.0126 9). Thirty seconds after the tetramethyl cyclotetrasiloxane addition, the reac-tion mixture exothermed t.o }84C. The reaction mixture was stirred for 2 hours at 80C then transferred to a te1On-coated mold containing 50.9 g woven glass cloth. The sample was cured for 12 hours at 130C, for eight hours at 160C, and for 16 hours at 180C to give an opaque, glassy plaque con-taining 60.7 wt. % glass cloth. This plaque was furthe~ cured in a N2 flushed oven at 200C, 250C and 310C for 4 hours at each temperature.
Example 8 This exampie show preparation of a molded, opaque solid plaques comprising a novel thermoset polymer per this inven~
tion, by preparing a B stage prepolymer by partially reacting dicyclopentadiene and tetramethyl cyclotetrasiloxane ,(ratio of carbon-carbon double bonds to hydrosilane groups of 1:1), transferring the B stage prepolymer into a mold, and heating to complete polymerization.
Following the general procedure in ~xample 4, tetra-methylcyclotetrasiloxane (76.36 9, 0.32 mole) was added to a heated (30C) mixture of dicyclopentadiene (83.9 g, 0.64 mole) and H2PtC16~6H2o (0.0148 g). Five minutes after this addition the reaction mixture exothermed to 193~C. The 25 reaction mixture was stirred for 1 hour at 55 to 70C, trans-ferred to teflon-coated molds and cured at 145C for 18 hours under slight vacuum. The opaque solid plaques were further cured to 285C in a N2 flushed oven.
The polymers of Examples 7 and 8 were further subjected to mechanical analysis to determine their glass transition temperature (Tg) and storage modulus (G') at various tempera-tures. Results are recorded in the following table.
~LZ,~73 Mechanical Analysis Wt. ~ TgG' (GPa) at T (C) Example(l) Glass (C)25 100 1~0 180 200 7(a) 60.7 2752.7 2.2 2.0 1,8 1.6 5(b) 60.7 3002.5 2.1 1.8 1.5 1.~
8(a) 0 2450.8 0.57 0.50 0.~3 0.35 (b) 0 2500.78 0.60 0.50 0.40 0.35 (1) a Deno~es data before water boil.
b Denotes data after 5 day water boil.
The data in this table demonstrate the relative water insensitivity of the organosilicon polymers of this inven-tion. The weight gained after 5 days in boiling water was about 0.1~.
Example 9 This example shows preparation of a novel thermoset polymer per this invention by reacting a dicyclopentadiene-oligomer ~omprising about 58.43% dicyclopentadiene, 43.75~
tricyclopentadiene and 5.05% tetracyclopentadiene (analyzed by G.C.), and tetramethylcyclotetrasiloxane (ratio of carbon-carbon double bonds to hydrosilane groups of 0.86:1).
A complex of 0.0076 g Of H2PtC16 6H20 and 21.71 g (0.12 mole) of the dicyclopentadiene oligomer was prepared by heating the two materials under a dry nitrogen blanket for one hour at 50C. Tetramethylcyclotetrasiloxane (16.10 g, 0.07 mole) was added to the yellow complex (complex temperature was 71C). The reaction exothermed to 153C in 8 seconds. The yellow solution was cooled to 30C, poured into Teflon coated slotted molds and cured at 150C/16 hours and 200C/~ hours.
The 112" x 3" x 1/8" test pieces were removed from the mold and post cured at 100C/0.5 hoursl 150C/0.5 hours, 200C/2 hours, 225C/2 hours, 250C/2 hours and 280/16 hours.
The final polymer was a hard glassy solid with a glass transition temperature of 250C and the weight loss by thermogravimetric analysis started at 500C.
.~.Z,~13~7~3 Example 10 This example shows the preparation of a molded article comprising a novel thermoset polymer per this invention, by partially reacting dicyclopentadiene ancl tetramethylcyclo-tetrasiloxane (ratio o~ carbon-carbon double bonds to hydro-silane groups of 1:1) to form a ~ stage type prepolymer, injecting the B stage prepolymer into a mold, and heating to complete polymerization.
The catalyst H2PtC16~6H20 (0.0148 g) was charged to a dried 25 oz. reaction vessel and sealed. Under a ni~ro~
gen blanket 83.95 g (0.635 mole) dicyclopentadiene was charged by syringe. The catalyst and dicyclopentadiene were heated for 90 minutes at 60 to 70C giving a yellow solution which was cooled to 30C. Tetrameth~lcyclotetrasiloxane (76.36 g, 0.317 mole) was added and an exothermic reaction started in two minutes, eventually reaching 193C. After cooling to 55C, a s~mple was injected into a 5" x 5" x 1/8" teflon lined aluminum mold. The polymer was polymerized at temper-atures ranging from 120 to 280C under a blanket of nitrogen.
Some electrical properties of the cured polymer are given below:
Dielectric Constant 2.87 60 Hz 2.83 1 MHz Dissipation 0.0001 60 Hz 25 Factor 0.0002 100 KHz Volume Resistivity ohm-cm 1.6 x 1ol8 Dielectric 381 Strength v/mil A sample of the Example 10 polymer was immersed in boil-ing water for five days. The sample weight increased 0.1%.
The dimensions of the sample (6.75, 1.30 cm, 0.32 cm) were unchanged after the boiling water treatment. The modulus/
temperature curve and glass transition temperature (250C) were also unchanged by the boiling water treatment.
Example_ll This example shows preparation of a novel thermoset poly-mer per this invention by reacting dicyclopentadiene and a mixture of methylhydrocyclosiloxanes, with a ratio o~ carbon-carbon double bonds to hydrosilane groups of 0,7:1.
Chloroplatinic acid (0.0035g) was weighed into an 8 oz.
reaction vessel under a nitrogen blanket in a dry box and the septum was sealed. Dry dicyclopentadiene (8.08g) was injected into the reaction vesse~ by a hypodermic syringe. The con-tents of the reaction vessel were heated to 60 to 65C for 1hour, under a nitrogen blanket, and the chloroplatinic acid dissolved. Dry air was swept through the reaction vessel for lo to 15 minutes and the contents were cooled to 31C.
Methylhydrocyclosiloxanes, consisting of 54% tetramethyl cyclotetrasiloxane, 20~ pentamethyl cyclopentasiloxane, 5%
hexamethyl cyclohexasiloxane, 19% higher methylhydrocyclo-siloxanes (up to approximately ((CH3(H)SiO-)20), and 2%
linear methylhydrosiloxanes, (total 11.93g) were injected and the reaction exothermed to 179C. After cooling the reaction product to 60C, it was poured into a teflon coated stainless steel mold. The mold was placed into a vacuum oven and a vacuum applied (approximately 15 mm Hg pressure, vacuum pump) for 10 to 15 minutes. Then, the mold was heated under nitro-gen for 6 hours at 180C, for 6 hours at 225C, for 2 hours at 235C, and for 4 hours at 285C.
The polymer of this example exhibits thermoset behavior when polymerized at 225C. The polymer does not have a melt-ing point, but softens at 100C to a soft extendable elasto-; mer. The polymer is a tough, leathe~ like solid at room temperature. It is flexible enough to be twisted 360 beforetearing.
Example 1~
This example shows preparation of a novel thermoset poly-mer per this invention by reacting dicyclopentadiene and methylhydrocyclosiloxanes in the same manner as in example 11, except that the monomers were used in amounts such that the . . --19--ratio of carbon-carbon double bonds to hydrosilane groups was 0.85:1 and the final heating was for 15 hours at 130C, for 6 hours at 160C, for 16 hours at 180C, for 4 hours at 200C, and for 4 hours at 225C.
The thermoset polymer formed after heating to 225C was tougher than that from example 11~ This hard, solid polymer maintains a high modulus up to 200C and exhibits elastomeric behavior when heated to 235C.
Exampl _ ThiS example shows preparation of a novel thermoset poly mer per this invention by reacting dicyclopentadiene and methylhydrocyclosiloxanes in the same manner as in example 11, except that the monomers were used in amounts such that -the ratio of carbon-carbon double bonds to hydrosilane groups of 1.15:1 and the final heating was for 4 hours at 150C, for 2 hours at 235C, and for 4 hours at 285C.
Example 14 This example shows preparation of a novel thermoset poly-mer per this invention by reacting dicyclopentadiene and methylhydrocyclosiloxanes in the same manner as in example ; 13, except that the monomers were used in amounts such that the ratio of carbon-carbon double bonds to hydrosilane groups of 1.30:1.
All the polymers produced in examples 12 to 14 exhibited thermoset characteristics and did not melt or lose their shape at temperatures below the decomposition points of the polymers (400 to 500C). Polymers prepared from reactants having a carbon-carbon double bond:hydrosilane equivalents ratio near 1:1 were post-cured at 285 to 300C to increase their glass transition temperature to the 260 to 300C range. The cross-link density of such polymers was high enough to prevent seg-mental motion and network deformation.
~Z~7~
Example 15 This example shows preparation of a novel thermoset poly-mer per this invention by reacting dicyclopentadiene and methylhydrocyclosiloxanes in the same manner as in example 11, except that the monomers were used in amounts such that the ratio of carbon-carbon double bonds to hydrosilane groups was 1.46:1 and the final heating was for 6 hours at 150C, for 6 hours at 200C, Eor 2 hours at 235C, and for 4 hours at 285C.
Example 15 demonstrates polymerization in the transition range from thermoset behavior to thermoplastic behavior. When polymerized up to 200C, the sample so~tened to a highly com pressible elastomer at about 120 to 125C. When the sample was post-cured at 285C, the glass transition temperature was raised to only 200C. The degree of crosslinking was limited by available hydrosilane yroups.
ExamE~e 16 This example shows preparation of a novel thermoplastic polymer per this invention by reacting dicyclopentadiene and methylhydrocyclosiloxanes in the same manner as in example 11, except in amounts such that the ratio of carbon-carbon double bonds to hydrosilane groups was 1.61:1 and the final heating was for 6 hours at 150C, for 6 hours at 2003C, for 8 hours at 235C, and for 4 hours at 285C.
Exam~le 17 This example shows preparation of a novel thermoplastic polymer per this invention by reactlng dicyclopentadiene and methylhydrocyclosiloxanes in amounts such that the ratio of carbon-carbon double bonds to hydrosilane groups was 1.75:1.
A catalyst solution containiny 600 ~pm chloroplatinic acid was prepared by heating 0.0953g of chloroplatinic acid with 158.8g dicyclopentadiene to 70C for 1.5 hours in a sealed 8 ounce reaction vessel, under nitrogen. A 150 ppm chloroplatinic acid solution was prepared by diluting 30g of 7~
the above catalyst solution with 90g of dicyclopentadiene. A
portion of the resultant chloroplatinic acid solution (7.92g) was weighed into a 7 inch reaction vessel with 4.59g of dicy-clopentadiene, making a 95 ppm concentration of chloroplatinic acid in dicyclopenta~iene (0.185 gram equivalent of olefin~.
Then, 7.21 g (0.106 hydrosilane equivalents) of methyl-siloxanes (described in example 11) were injected into the sealed reaction vessel at 23C. The reaction mixture was - heated to 36C and a slight exotherm raised the temperature to 60C, where the mixture became viscous. A vacuum (15 mm Hg) was applied to the contents of the reaction vessel at 45C for 10 minutes to pull gas out of the reaction product. The product was poured into a teflon coated stainless steel mold and heated in a nitrogen blanket for 6 hours at 150C, for 20 hours at 200C, and for 6 hours at 225 to 235~C. The 3" x 1/2" x 1/8" specimens removed from the mold were transparent, hard solid with a melting point of 117 to 125C. This solid could be ground into a crystalline powder.
The polymers of examples 16 and 17 do not form a com-plete polymeric network, even when they are polymerized at 225 to 235C. They are completely thermoplastic and form a viscous, flowable liquid above their melting points. The solids can be ground into powder.
The properties of the polymers prepared in examples 11 to 17 are shown in the following Table.
-22~ 73 .
r~ "~ O ~
~ ~ .
nl~
~I r~ a~ o u u O ~ ~ O _~
A . O
r~ rl n ,~
! ~ ~ ,. ~ o u~ o 1~ o o I~ s ~,~ ~ . u ~ ~ ~ u o ~ I o O ,~ o ~ ,n O ~ 1 1 U
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r~ O U- 111 Ul O O I I I r ~ UO O Cl-~ o o o ~ o f3~ e ~, ~ ~ 2 ~ h U ~U
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Example 18 This example shows preparation of graphite fiber com-posite.
Chloroplatinic acid (0.0185g) was weighed into a reac-tion vessel in a dry box and the reaction vessel was sealed.Dicyclopentadiene (47.15g, 0.357 mole, 0.714 equivalents) was injected into the reaction vessel and the mixture was heated with stirring to 60C for 1 hour. After cooling to 36C, tetramethylcyclotetrasiloxane ~44.67g) was injected. In two minutes, the sample exothermed to 192C. The product was cooled and injected into a teflon lined mold 5" x 5" x 1/8"
containing ten 5" x 5" sheets of square woven graphite fiber cloth. The loaded mold was heated in a nitrogen blanketed oven for 15 hours at 130C, for 6 hours at 160C, and for 12 hours at 180C. The resulting composite had good flexural strength t68,000 psi) and modulus (4.7 x 106 psi).
Claims (31)
1. A crosslinked or crosslinkable organosilicon polymer, characterized in that it comprises alternating polycyclic hydrocarbon residues and cyclic polysiloxanes or siloxysilane residues linked through carbon to silicon bonds, said polymer being the reaction product of (a) a cyclic polysiloxane or a tetrahedral siloxysilane containing at least two hydrosilane groups and (b) a polycyclic polyene having at least two nonaromatic carbon-carbon double bonds in its rings, wherein the ratio of carbon-carbon double bonds in the rings of (b) to hydrosilane groups in (a) is in the range of from greater than 0.5:1 up to 1.8:1, and at least one of (a) or (b) has more than two reactive sites.
2. A crosslinked or crosslinkable organosilicon polymer as claimed in claim 1, further characterized in that the silicon-containing reactant is:
(I) wherein R, which can be the same or different, is hydrogen, a saturated, substituted or unsubstituted alkyl or alkoxy radical, a substituted or unsubstituted aromatic or aryloxy radical, n is an integer from 3 to about 20, and R is hydrogen on at least two of the silicon atoms in the molecule; or is:
(II) wherein R is as defined above and is hydrogen at least two silicon atoms in the molecule.
(I) wherein R, which can be the same or different, is hydrogen, a saturated, substituted or unsubstituted alkyl or alkoxy radical, a substituted or unsubstituted aromatic or aryloxy radical, n is an integer from 3 to about 20, and R is hydrogen on at least two of the silicon atoms in the molecule; or is:
(II) wherein R is as defined above and is hydrogen at least two silicon atoms in the molecule.
3. A crosslinked or crosslinkable organosilicon polymer as claimed in claim 1 or 2, further characterized in that the polycyclic hydrocarbon residues are divalent saturated residues based on norbornadiene.
4. A crosslined or crosslinkable organosilicon polymer as claimed in claim 1 or 2, further characterized in that the polycyclic hydrocarbon residues are divalent saturated residues based on dicyclopentadiene.
5. A crosslinked or crosslinkable organosilicon polymer as claimed in claim 1 or 2, further characterized in that the silicon-containing residues are polyvalent residues based on a cyclic polysiloxane or a mixture of cyclic polysiloxanes.
6. A crosslinked or crosslinkable organosilicon polymer as claimed in claim 1 or 2, further characterized in that the silicon-containing residues are polyvalent residues based on a tetrahedral siloxysilane or a mixture of tetrahedral siloxy-silanes.
7. A crosslinked or crosslinkable organosilicon polymer as claimed in claim 1 further characterized in that the poly-cyclic polyene is norbornadiene, dicyclopentadiene, tricyclo-pentadiene, hexahydronapthalene, dimethanohexahydronaphthalene, or norbornadiene dimer.
8. A crosslinked organosilicon polymer as claimed in claim 1 or 2, further characterized in that the ratio of carbon-carbon double bonds in the rings of (b) to hydrosilane groups in (a) is in the range of from about 0.7:1 up to about 1.3:1, and the alternating residues form a crosslinked thermo-set structure.
9. A crosslinked organosilicon polymer as claimed in claim 8, further characterized in that the ratio of carbon-carbon double bonds in the rings of (b) to hydrosilane groups in (a) is in the range of from about 0.8:1 up to about 1.1:1.
10 . A crosslinkable organosilicon polymer as claimed in claim 2, further characterized in that it is thermoplastic and the ratio of carbon-carbon double bonds in the rings of (b) to hydrosilane groups in (a) is in the range of from greater than 0.5:1 up to about 0.7:1, or in the range of from about 1.3:1 up to about 1.8:1.
11. Use of the organosilicon polymer as claimed in claim 1 or 2,in a fiber reinforced composite structure com-prising up to 80%, by weight of a fibrous reinforcement.
12 . Use as claimed in claim 11 of the organosilicon polymer, further characterized in that the fibrous reinforcement is glass, carbon, metallic, ceramic, or synthetic polymer fibers, or a fiber mat.
13 . A method for preparing the organosilicon polymers as claimed in claim 1 or 2, characterized in that it comprises reacting, in the presence of a hydrosilation catalyst, (a) a cyclic or tetrahedral polysiloxane containing at least two hydro-silane groups and (b) a polycyclic polyene having at least two non-aromatic carbon-carbon double bonds in its ring, the ratio of carbon-carbon double bonds in (b) to hydrosilane groups in the rings of (a) being in the range of from greater than 0.5:1 up to 1.8:1 and at least one of (a) or (b) having more than two reactive sites, and subjecting said polymer to heat to drive the crosslinking to a maximum.
14. A method for preparing organosilicon polymers as claimed in claim 13, further characterized in that the cyclic or tetrahedral polysiloxane containing at least two hydrosilane groups is:
(I) wherein R in hydrogen, a saturated, substituted or unsubstituted alkyl or alkoxy radical, a substituted or unsubstituted aromatic or aryloxy radical, n is an integer from 3 to about 20, and R
is hydrogen on at least two of the silicon atoms in the molecule;
or is:
(II) wherein R is as defined above and is hydrogen at at least two silicon atoms in the molecule.
(I) wherein R in hydrogen, a saturated, substituted or unsubstituted alkyl or alkoxy radical, a substituted or unsubstituted aromatic or aryloxy radical, n is an integer from 3 to about 20, and R
is hydrogen on at least two of the silicon atoms in the molecule;
or is:
(II) wherein R is as defined above and is hydrogen at at least two silicon atoms in the molecule.
15. A method for preparing organosilicon polymers as claimed in claim 13 further characterized in that the ratio of carbon-carbon double bonds in (b) to hydrosilane groups in the rings of (a) is in the range of about 0.7:1 up to about 1.3:1.
16. A method for preparing organosilicon polymers as claimed in claim 15 further characterized in that the ratio of carbon-carbon double bonds in the rings of (b) to hydrosilane groups in (a) is in the range of from about 0.8:1 up to about 1.1:1.
17. A method for preparing organosilicon polymers a claimed in claim 13 , wherein the hydrosilation catalyst is selected from metal salts and complexes of Group VIII elements.
18 . A method for preparing organosilicon polymers as claimed in claim 13, wherein the hydrosilation catalyst is a platinum-containing catalyst.
19 . A method for preparing organosilicon polymers as claimed in claim 13, wherein the hydrosilation catalyst is selected from the group consisting of chloro-platinic acid, PtCl2 and dibenzonitrile platinum dichloride.
20 . A method for preparing organosilicon polymers as claimed in claim 13, wherein the hydrosilation catalyst is chloroplatinic acid.
21. A method for preparing organosilicon polymers as claimed in claim 13, further characterized in that it includes the steps of: (i) partially reacting (a) and (b) to form a prepolymer or oligomer; (ii) impregnating the pre-composite or a filler; mixing the prepolymer or oligomer with a substance for forming a composite or a filler; or transferring the prepolymer or oligomer into a substance for forming a com-posite, onto a filler or onto a substrate for forming a film or coating, or to a mold; and (iii) curing the prepolymer or oligomer to form a thermoset product.
22. A method for preparing organosilicon polymers as claimed in claim 21, further characterized in that the pre-polymer of oligomer is a liquid formed by heating (a) and (b) until about 30 to 50% of the carbon-carbon and hydrosilane groups are reacted.
23. A method for preparing organosilicon polymers as claimed in claim 13, further characterized in that step (ii) is transferring the prepolymer or oligomer to a mould containing in an amount of up to 80%, by weight, fibrous reinforcement.
24. A crosslinkable liquid prepolymer or oligomer characterized in that it comprises alternating polycyclic hydro-carbon residues and cyclic polysiloxanes or siloxysilane resi-dues linked through carbon to silicon bonds.
25, A crosslinkable organosilicon polymer as claimed in claim 24 further characterized in that it is the reaction product of (a) a cyclic polysiloxane or n tetrahedral siloxy-silane containing at least two hydrosilane groups and (b) a polycyclic polyene having at least two non-aromatic carbon-carbon double bonds in its rings, wherein the ratio of carbon-carbon double bonds in the rings of (b) to hydrosilane groups in (a) is in the range of from greater than 0.5:1 up to 1.8:1, and at least one of (a) or (b) has more than two reactive sites.
26 . A crosslinkable organosilicon polymer as claimed in claim 25, further characterized in that the silicon-containing reactant is:
(I) wherein R, which can be the same or different, is hydrogen, a saturated, substituted or unsubstituted alkyl or alkoxy radical, a substituted or unsubstituted aromatic or aryloxy radical, n is an integer from 3 to about 20, and R is hydrogen on at least two of the silicon atoms in the molecule; or is:
(II) wherein R is as defined above and is hydrogen at least two silicon atoms in the molecule.
(I) wherein R, which can be the same or different, is hydrogen, a saturated, substituted or unsubstituted alkyl or alkoxy radical, a substituted or unsubstituted aromatic or aryloxy radical, n is an integer from 3 to about 20, and R is hydrogen on at least two of the silicon atoms in the molecule; or is:
(II) wherein R is as defined above and is hydrogen at least two silicon atoms in the molecule.
27 . Use of the organosilicon polymer as claimed in claim 1 or 2 as a coating.
28 . Use of the organosilicon polymer as claimed in claim 1 or 2 as a coating for glass.
29 . Use of the organosilicon polymer as claimed in claim 1 or 2 as a film.
30 . A crosslinked or crosslinkable organosilicon polymer as claimed in claim 1 or 2, further characterized in that it contains a filler in amount of up to 80%.
31 . A crosslinked or crosslinkable organosilicon polymer as claimed in claim 1 or 2 , further characterized in that it contains a pigment.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US90109286A | 1986-08-27 | 1986-08-27 | |
| US901,092 | 1986-08-27 | ||
| US079,740 | 1987-07-30 | ||
| US07/079,740 US4900779A (en) | 1986-08-27 | 1987-07-30 | Organosilicon polymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1295773C true CA1295773C (en) | 1992-02-11 |
Family
ID=26762377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000545252A Expired - Lifetime CA1295773C (en) | 1986-08-27 | 1987-08-25 | Organosilicon polymers |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4900779A (en) |
| EP (1) | EP0259711B1 (en) |
| KR (1) | KR0134785B1 (en) |
| AU (1) | AU593676B2 (en) |
| BR (1) | BR8704416A (en) |
| CA (1) | CA1295773C (en) |
| DE (1) | DE3789475T2 (en) |
| ES (1) | ES2060588T3 (en) |
| HK (1) | HK110394A (en) |
| MX (1) | MX173700B (en) |
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-
1987
- 1987-07-30 US US07/079,740 patent/US4900779A/en not_active Expired - Lifetime
- 1987-08-25 CA CA000545252A patent/CA1295773C/en not_active Expired - Lifetime
- 1987-08-25 MX MX790587A patent/MX173700B/en unknown
- 1987-08-26 AU AU77461/87A patent/AU593676B2/en not_active Ceased
- 1987-08-27 DE DE3789475T patent/DE3789475T2/en not_active Expired - Lifetime
- 1987-08-27 EP EP87112491A patent/EP0259711B1/en not_active Expired - Lifetime
- 1987-08-27 ES ES87112491T patent/ES2060588T3/en not_active Expired - Lifetime
- 1987-08-27 KR KR1019870009455A patent/KR0134785B1/en not_active IP Right Cessation
- 1987-08-27 BR BR8704416A patent/BR8704416A/en not_active IP Right Cessation
-
1994
- 1994-10-12 HK HK110394A patent/HK110394A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0259711A3 (en) | 1989-11-29 |
| AU7746187A (en) | 1988-03-03 |
| EP0259711B1 (en) | 1994-03-30 |
| DE3789475D1 (en) | 1994-05-05 |
| MX173700B (en) | 1994-03-23 |
| ES2060588T3 (en) | 1994-12-01 |
| DE3789475T2 (en) | 1994-07-14 |
| AU593676B2 (en) | 1990-02-15 |
| KR880002916A (en) | 1988-05-12 |
| MX7905A (en) | 1993-10-01 |
| EP0259711A2 (en) | 1988-03-16 |
| HK110394A (en) | 1994-10-21 |
| US4900779A (en) | 1990-02-13 |
| KR0134785B1 (en) | 1998-04-20 |
| BR8704416A (en) | 1988-04-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |