CN100575403C - The liquid hard plastics - Google Patents
The liquid hard plastics Download PDFInfo
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- CN100575403C CN100575403C CN02829252A CN02829252A CN100575403C CN 100575403 C CN100575403 C CN 100575403C CN 02829252 A CN02829252 A CN 02829252A CN 02829252 A CN02829252 A CN 02829252A CN 100575403 C CN100575403 C CN 100575403C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
By in rigid plastics, add the pyrolysis method preparation, with the silicon-dioxide of the silane modified surface that comprises the methacrylic acid group, prepared enhanced liquid hard plastics.
Description
Technical field
The present invention relates to the method for a kind of enhance liquid rigid plastics (duroplastics), and relate to resulting rigid plastics.
Summary of the invention
Rigid plastics is meant all plastics by curable resins.According to DIN 7724, they be crosslinked, near cancellated, high polymeric material, up to decomposition temperature, it is steel-elastic at low temperatures and shows as very limited elastic deformability between 50 ℃ or higher temperature and decomposition temperature.Also be reduced to 10 under the not meeting in its shearing modulus under any temperature
2Kp/cm
2
Rigid plastics is normally unbodied.Because rigid plastics is crosslinked, their molecule can not carry out any macroscopic pedesis.On the other hand, the pedesis of polymer molecule microcosmic is possible at the second-order transition temperature that is higher than 50 ℃.
Term rigid plastics and title duromer (duromer) are equal to, and preferably being called duromer sometimes is because it is with more tight in the contact aspect the form as the elastomerics and the plastomer (thermoplastics) of two kinds of different sorts plastics signs.
Rigid plastics is widely used as moulding compound, casting resin, resin glue and coating resins.(abbreviation is according to DIN 7728 particularly including commercially important material for rigid plastics, P1, on January 1st, 1988, represent with parantheses): diallyl phthalate ester resin (DAP), epoxy-melamine formaldehyde resin (MF), trimeric cyanamide-phenol-formaldehyde resin (MP), phenol-formaldehyde resin (PF) and unsaturated polyester resin (UP).
Using powdered silicon-dioxide is well-known as the filler of polymkeric substance.
Usually, with by the filler of the cingens hard phase form fine distribution of flexible polymer, improved the mechanical property of many commercially valuable materials.These comprise hardness, tensile strength, stress value and other measurable performances.
In principle, between thermoplastic polymer and crosslinkable polymer, certainly existing and distinguishing.Silicon-dioxide can be used as filler in two class materials.Yet because polymkeric substance, the amount that is added may be very different with effect.
Using silicon-dioxide in the liquid hard plastics also is well-known as thickening material.Yet that is not this subject matter of an invention; On the contrary, the thickening power of silicon-dioxide should be as far as possible little.
The invention describes use with the silicon-dioxide of the unsaturated organic group modification in the lower molecular weight reactive polymer (being generally liquid).It shows that the favourable combination of reaching rheologic behavio(u)r and mechanical property is possible,, has low viscosity and low flow limitation on the one hand under uncrosslinked state that is, has high hardness and high modulus on the other hand under crosslinked state.
In order in crosslinked product, to obtain favourable performance, be well-known with the filler that uses in vinyl silanes or the methacrylic acid silane treatment polymkeric substance.This processing is carried out according to prior art in the process that filler is mixed into polymkeric substance.
The shortcoming of this program is to occur in the environment that is difficult to control for silane necessary chemical reaction sequence with solid is connected that hope obtains, and its reproducibility also makes us dissatisfied.And, form as inevitable waste product alcohol; That alcohol does not normally wish to obtain as the composition of polymer materials and must remove with complicated operations.
Silane itself and formed therefrom split product are the sources of a danger and need extra security measures and investment usually for flammable and toxicity.Therefore the hope use is a kind of has comprised the desired response group and can not discharge any filler of not wishing material to polymkeric substance or environment.
Summary of the invention
The invention provides a kind of method of enhance liquid rigid plastics, the method is characterized in that the mixture of the silicon-dioxide of the pyrolysis method preparation that has prepared uncrosslinked resin and used the silane modified surface that contains the methacrylic acid group.
The present invention also provides the liquid hard plastics, it is characterized in that they comprise the silicon-dioxide of the pyrolysis method preparation of using the silane modified surface that comprises the methacrylic acid group.
In a specific embodiments of the present invention, the silicon-dioxide of pyrolysis method preparation can be modification on the structure.
According to the present invention, especially effectively filler be to comprise the methacrylic acid group and be by the flame hydrolysis preparation and also its structure after processing by mechanical alteration silicon-dioxide.
Can be used for the silicon-dioxide of pyrolysis method preparation of the present invention, its feature is as follows:
BET surface-area m
2/ g 20～380
Size of particles nm 6～110
Tamped density g/l 50～600
PH value 3～10
Carbon content % 0.1～15
DBP value %＜200
It can be by at first being mixed with silicon-dioxide and water or diluted acid and then with surface-modifying agent in suitable mixing device consumingly, and perhaps the mixture that is coated with last layer different surfaces properties-correcting agent by spraying prepares.Each component is further mixed, and the time heat-treated under 100～400 ℃ temperature 1～6 hour then from 15～30 minutes.
In a preferred embodiment of the invention, the silicon-dioxide of pyrolysis method preparation can be used as silicon-dioxide.
Pyrogenic silica prepares by the flame hydrolysis of volatile silicon compound, for example, and SiCl
4, METHYL TRICHLORO SILANE etc.The preparation method can be from Ullmann's
Dertechnischen Chemie, the 4th edition, 21 volumes, learn the 464th page (1982).
In a preferred embodiment of the invention, can use and have about 200m
2The pyrogenic silica of/gBET surface-area.
As surface-modifying agent, can use monomeric substance, methacryloxypropyl trialkoxy silane for example, wherein alkoxyl group can be methoxyl group, oxyethyl group and/or propoxy-.
The essential characteristic of described invention is a filler and oligopolymer being connected by photopolymerization reaction of reactive monomer and lacquer.
Find surprisingly, for concrete liquid resin system, even under unglazed condition, comprise the methacrylic acid group and by flame hydrolysis preparation and also its structure after processing, can be produced uneven hard polymkeric substance by the silicon-dioxide of mechanical alteration, can distinguish by favourable performance.
The example of this resin system is:
The unsaturated polyester resin of various compositions:
A. ethylenic unsaturated polyester,
B. with the ethylenically unsaturated monomers of A copolymerization,
C. with A+B the fiber enhancer of benchmark, 5～300 weight %,
D. Ren Xuan fleut,
E. with A+B the thickening material of benchmark, optional 0.5～5 weight %,
F. with A+B the organo-peroxide of benchmark, 0.5～5 weight %,
G. aromatic amine, organic acid metal-salt, for instance, cobalt compound,
H. the conventional additive of Ren Xuan other.
A. as unsaturated polyester, but suitable is by polybasic, particularly binary carboxylic acid and the formed conventional polycondensation product of their esterified derivative (particularly acid anhydride), its mode with ester links to each other with poly-hydroxy especially dihydroxy alcohol, and optional comprise the group of single hydroxyl alcohol and/or the group of hydroxycarboxylic acid in addition, but wherein at least some groups must have the undersaturated copolymerization group of ethylenic.
As polyhydric, dihydric optional unsaturated alcohol particularly, suitable is conventional alkane diol and the oxa-alkane diol that has acyclic or cyclic group, for example, 1,2-ethylidene glycol, 1,2-propylene glycol, 1, ammediol, 1,3 butylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, 2,2-dimethylene-1, ammediol, glycol ether, Diethylene Glycol, polyoxyethylene glycol, a propylene glycol, 1 that contracts, 2-cyclohexanediol, 2, two (hydroxyl-cyclohexyl)-propane of 2-, TriMethylolPropane(TMP) mono allyl ether or 1, the 4-butyleneglycol.
Also can follow the list that uses minor amount-, three-or the alcohol of higher hydroxyl, for example, ethylidene hexanol, Fatty Alcohol(C12-C14 and C12-C18), phenylcarbinol, 1,2-two-(allyloxy)-propyl alcohol-(3), glycerol, tetramethylolmethane or TriMethylolPropane(TMP).It is polyhydric, particularly but dihydric alcohol is usually with the carboxylic acid of stoichiometric amount and polybasic, particularly binary or the derivatives reaction of their condensations.
Suitable carboxylic acid and their derivative have binary, olefinic is undersaturated, be preferably the undersaturated carboxylic acid of β-olefinic, for example, maleic acid, FUMARIC ACID TECH GRADE, chloromaleic acid, methylene-succinic acid, methylene radical pentanedioic acid and methylfumaric acid and their ester or be preferably their acid anhydride.Also may be suitable for other binary in addition, undersaturated and/or saturated and fragrant pass through the carboxylic acid that modified-reaction is condensed into polyester, for example, Succinic Acid, pentanedioic acid, methylglutaric acid, hexanodioic acid, sebacic acid, pimelic acid, Tetra hydro Phthalic anhydride, phthalic acid, m-phthalic acid, terephthalic acid, the dihydro phthalic acid, tetrahydrophthalic acid, tetrachloro is for phthalic acid, 3, methylene radical-1 in the 6-, 2,3, the 6-tetrahydrophthalic acid, interior methylene radical tetrachloro for methylene radical tetrahydrophthalic acid in phthalic acid or the hexachloro-and single-, three-and polybasic carboxylic acid more, for example, thylhexoic acid, lipid acid, methacrylic acid, vinylformic acid, propionyloxy 1,2,4, the 5-benzene tertacarbonic acid.Preferred maleic acid or its acid anhydrides and the FUMARIC ACID TECH GRADE used.
Also can use the unsaturated polyester that has prepared easily by Dicyclopentadiene (DCPD).
Also may use the mixture of unsaturated polyester, comprise that those have only crystalline limited solubility and easy in monomers B.This easy crystalline unsaturated polyester may be by for example FUMARIC ACID TECH GRADE, hexanodioic acid, terephthalic acid, ethylene glycol, 1,4-butyleneglycol, 1, and 6-hexylene glycol and neopentyl glycol are formed.
The acid number that unsaturated polyester has is 5～200, is preferably 20～85, and molecular-weight average is about 800～6000, is preferably about 1000～4000.
Unbodied and optional crystalline unsaturated polyester is made up of they initial according to continuous or discrete method usually that melt condensation is prepared under azeotropic conditions.
But B. Shi Yi copolymerization, the ethylenically unsaturated monomers compound is the allylic cpd that tradition is used for unsaturated polyester casting composition preparation, be preferably the compound of vinyl, vinyl aromatic compound for example is as vinylbenzene, methylene-benzene ethene, right-chlorostyrene or Vinyl toluene; Vinylformic acid and methacrylic acid and have the ester of the alcohol of 1～18 carbon atom, for example methyl methacrylate, butyl acrylate, vinylformic acid (ethyl hexyl) ester, vinylformic acid hydroxypropyl ester, dihydro dicyclopentadienyl acrylate, butylene glycol diacrylate and (methyl) acrylic acid amides; Allyl ester is as diallyl phthalate and vinyl ester, as thylhexoic acid vinyl ester, vinyl acetate, propionate, vinyl trimethylacetic acid ester and other.The mixture of the Shi Yi unsaturated monomer that also has above-mentioned olefinic in addition.What B was formed in preferred suitable conduct is vinylbenzene, Vinyl toluene and diallyl phthalate.Monomers B is included in the polyester casting composition with the amount based on 10～80 weight % that form A and B gross weight usually, is preferably 20～70 weight %.
C. as fortifying fibre, it is the inorganic or organic fibre that the form with rove or flat structures that suits exists, for example with glass, carbon fiber, asbestos, Mierocrystalline cellulose and synthetic organic fibre, for example the form of polycarboxylate, polycarbonate and polymeric amide exists, and therefrom optional woven fabric is as the pad seat.The amount of the fortifying fibre that uses is 5～300 weight % based on forming A+B, is preferably 10～150 weight %.
D. Shi Yi filler, for example, traditional meticulous powdery or granulous mineral filler, for example chalk, kaolin, silica powder, rhombspar, barite, metal powder, aluminium hydroxide, cement, talcum, diatomite, wooden powder, wood particle, pigment or the like.They are used for the SMC casting composition with the amount based on 0～200 weight % of A+B, are used for the BMC casting composition with the amount based on 100～400 weight % of A+B.
E. as thickening material, can be mention as alkaline-earth oxide or oxyhydroxide, the mixture of calcium oxide, calcium hydroxide, magnesium hydroxide and preferred magnesium oxide and their oxide compound or oxyhydroxide for example.Also can partly replace them with zinc oxide.Also suit under some occasion of polymeric polyisocyanate or metal alcoholate.Thickening material joins in the casting composition with the amount based on 0.5～5 weight % of A+B.
F. as the polymeric initiator,, be preferably the traditional organo-peroxide that can at high temperature produce free radical of amount use of 0.1～3 weight % with based on 0.05～5 weight % that forms A and B gross weight.Suitable initiator is for example: benzoyl peroxide, the tertiary butyl are crossed octylate, tertiary butyl perbenzoic acid salt, dicumyl peroxide, two uncle's dibutyl superoxide and are crossed ketal, and for example, trimethylcyclohexyl is crossed ketal and percarbonate.
G. other conventional additive is, for example, inhibitor, as Resorcinol, 2,6-dimethyl Resorcinol, tertiary butyl benzo pyrocatechol, right-benzoquinones, tetrachlorobenzoquinone, 2, salt of 6-phlorone, oil of mirbane such as m-dinitrobenzene, phenothiazine or N-nitroso-group-N-cyclohexyl azanol and composition thereof.Inhibitor is included in the casting composition with the amount based on 0.005～0.2 weight % that forms A+B usually, is preferably 0.01～0.1 weight %.
As the lubricant that can consider be, for example, the hard acid ester salt of zinc, magnesium and calcium and polyalkylene ether wax.
This kind polyester resin is known, for example, can learn from EP 0 120 272 A1.
Vinyl ester resin, be also referred to as the VE resin during as bezene acrylic acid resin (being abbreviated as PHA), be based on the reacting resin of phenyl (phenylene) derivative, for example, its alcohol groups by (methyl) acroleic acid esterification phenol or the aromatic glycidyl ethers of epoxidation novolak resin.
The resin of so-called " vinyl ester " this class is acknowledged as many years of suitable application as broad range of resins, and particularly those require higher application to chemical-resistant.Resin is the chemical reaction product of Resins, epoxy and the unsaturated product of olefinic of Resins, epoxy.Commercially available in the market typical ethylene base ester resin comprises EPOCRYL resin (Shell ChemicalCompany sale), DERKANE 411 (Dow Chemicals Company sale) and CO-REZYN VE-8300 (Itnerplastic Company sale).
Using vinyl ester resin to prepare in the process of shaping prod, particularly in glass filament reinforced plastics (FRP) structure, should control the viscosity of resin combination, make composition mobile be enough to allow simply to use, to good wetting of filler and strengthen, thereby can not cause resin to flow out the incomplete zone of the resin that produces the shaping prod simultaneously again from vertical surface.And, in a lot of purposes, for example on the purposes of the product that uses the vinyl ester resin preparation to be shaped such as pipe, case, washer or waste pipe, if production process is not had strict the qualification, so You Yi quality and support performance are just extremely important, particularly in the process of shaping and curing schedule.Under this application, resin is dissolved in vinyl monomer usually, as in the vinylbenzene and be shaped to solidify the preparation shaping prod.If, for example when resin combination being coated on the vertical surface as lining, be shaped and curing schedule during, the quality of composition and support performance make outflow that composition occurs or mobile, thereby cause the resin surface reduction in uneven thickness physical strength of shaping prod so.
Once proposed in the past by adding some thixotropic agent to improve viscosity, quality and the support performance of vinyl ester resin.It is reported that aerosil is that " very effective " thixotropic additive (is seen " Unsaturated Polyester Technology ", edited by Paul F.Gruins in some vinyl ester resin is formed; Gordon and Breach Science Publishers).
For processing, curing being become easily and desirable mechanical property being provided, composition of the present invention can comprise comonomer.Suitable compatible comonomer comprises the undersaturated comonomer of reactive, ethylenic, as vinylbenzene, chlorostyrene, Vinyl toluene, vinyl toluene, diallyl phthalate, cyanuric acid triallyl ester, acrylate, methacrylic ester and Vinylstyrene.Vinylbenzene is preferred compatible auxiliary.Composition also can comprise non-reacted thinner, and as acetone, the performance of wherein only using simple resin to obtain is desirable.
The vinyl ester resin that uses among the present invention can be any known in the art and by preparing by addition reaction between Resins, epoxy and the undersaturated monocarboxylic acid of ethylenic.US Patent specification the 3rd, 256,226,3,317,465,3,345,401,3,373,221,3,377,406,3,432,478,3,548,030,3,564,074,3,634,542 and 3,637, the method for the suitable vinyl ester resin of preparation is disclosed in No. 518.
Usually, the reaction of using among preparation the present invention that vinyl ester resin relied on is simple.It can by suitable catalyzer for example the salt catalysis of tertiary amine, phosphuret-(t)ed hydrogen, basic metal or this compounds finish.The common equation of reaction can be described below:
Wherein R for example is alkylidene group, ring alkylidene group, arylidene, inferior aralkyl, inferior oxygen aryl, inferior oxygen arylalkyl or cycloalkylidene ester.
Suitable acid is vinylformic acid, methacrylic acid, butenoic acid and styracin.Suitable Resins, epoxy is as follows:
In fact many different vinyl ester in conjunction with different qualities can prepare by different Resins, epoxy and different unsaturated acid are combined.The diversity of product is expansion certainly even further, and this depends on and can combine with vinyl ester resin and the selection of the unsaturated monomer of copolymerization.Having obtained the vinyl ester resin of maximum utility up to now and therefore being preferred for of the present invention is that bisphenol-A (BPA) epoxy is a vinyl ester resin.These resins can be used for composition of the present invention, perhaps have or do not have coreaction monomer such as vinylbenzene.
Except that vinyl ester resin, thixotropic additive and the reactive or non-reacted thinner that added if desired, resin combination of the present invention also can comprise catalyzer, inhibitor, filler, pigment and/or other known conventional additives.
Composition of the present invention can utilize the initiator of generation free radical well known in the art to carry out polymerization and crosslinked.The polymerization of resin relies on real addition reaction and does not have by product to form usually.Suitable initiator comprises superoxide, is preferably organo-peroxide, as benzoyl peroxide or methyl-ethyl-ketone peroxide and other radical source.For example, the light trigger of generation free radical also can be used for causing the polymerization of the present composition.Initiator can with traditional accelerator or promotor such as tertiary amine, for example dimethyl or Diethyl Aniline, and the octylate or the naphthenate of metallic soap such as cobalt or manganese use jointly.
Can use different manufacturing process to come the shaping resin composition.Suitable method comprises that manual shop layer method, cold press process, bag molding, match die process, filament twine method and progressive die method for making.
Acrylic resin can be the synthetic resins of cold or thermofixation, its by (methyl) acrylate (so-called pure-the copolymerization acquisition of A) homopolymerization or they and for example vinylbenzene or vinyl ester.The acrylic resin of thermofixation comprises functional group's (hydroxyl, methylol, carboxyl) that can carry out crosslinking reaction again; They are can the oneself crosslinked or carry out crosslinked (for example after adding aminoplastics or Resins, epoxy) by externalist methodology.The solubleness of acrylic resin and mechanical property can extensively change by monomeric selection.The solidified acrylic resin is UV resistant and non-discoloring transparent products normally.
The coating resin of cold-curing has following component, for example:
A) (methyl) acrylate 50～100 weight %
(methyl) methyl acrylate 0～5 weight %
(methyl) ethyl propenoate 0～5 weight %
C
3-C
6(methyl) acrylate 0～97 weight %
〉=C
7(methyl) acrylate 0～50 weight %
Polybasic (methyl) acrylate 3～10 weight %
Comonomer 0～50 weight %
Vinyl aromatic compound 0～30 weight %
Vinyl ester 0～30 weight %
The composition total amount of component A is 100 weight %,
What the B) A of per 1 weight part) comprise 0～2 weight part is dissolvable in water or swells in A) (in advance) polymkeric substance, the amount of (methyl) methyl acrylate or (methyl) ethyl propenoate on the basis of B＞5 weight %,
C) (A+B) of per 100 weight parts comprises at least a paraffin and/or the wax of 2～5 weight parts,
D) redox system, its (at least for a kind of composition in the redox system) keeps separately, up to the polymerization of the polymerizable composition that is used for system, this redox system comprises the accelerator that is used for composition A cold-curing and the snperoxiaized catalyzer or the initiator of q.s, and
E) traditional additive.
In order to obtain the combination of seeing especially favourable performance from commercial point of view, hybrid resin can be the mixture of vibrin and vinyl ester and/or acrylic resin.
Resin and silicon-dioxide and solidifying agent and the optional accelerator that adds are wherein carefully mixed.The temperature that curing can at room temperature be set, carry out in room temperature range or in the design temperature scope that is higher than room temperature, this depends on solidifying agent.The qualification of top temperature is determined for example monomeric vapour pressure by the physical-chemical data of resin usually.
The rigid plastics that comprises the silicon-dioxide that contains acrylic acid groups of modification on the structure of the present invention can be liquid, pasty state or solid form.
They can comprise: the powdery of interpolation or the packing material of fiber as: the fluid additive of silica powder, glass fibre, pigment, fire retardant, metal oxide, metal powder, graphite, carbon black or solvent version, softening agent, non-reacted interpolation resin such as hydrocarbon resin, give flexible resin and phenol resins, wax, reagent and additive in polymerization and adhesion promoters.
Other additive can be: thickening material, whipping agent, releasing agent, be used to increase the stablizer in work-ing life.
The silicon-dioxide that the present invention uses comprise the methacrylic acid group and by flame hydrolysis preparation and its structure after handling by mechanical alteration, it is for having brought many technical superioritys according to resin of the present invention and the goods that prepare therefrom.
Form contrast with the silicon-dioxide of known fine dispersion, its thixotropic transformation is very low.This correspondence is used and the loss behavior of coating and tackiness agent preparation is very favorable.
The bond formation cross-linking set that reacts between the polymerization period of acrylic-functional at reaction resin of solid surface is given final product very hardness, intensity and the elasticity of high level so securely.In addition, the speed of crosslinking reaction may increase, and makes coating dust-dry more promptly, thereby laminated product can earlier break away from from mould.
Equally, improved the processing of moulding compound, particularly at high infill system, the reactivity of silicon-dioxide of the present invention influences under the identical situation in the solidification process of molding in the short period of time.
Of the present inventionly comprise the methacrylic acid group and during by the silicon-dioxide of flame hydrolysis preparation, a special advantage is not have free alcohol to form equally in preparation when using, and this be when use inevitable during according to the liquid silane of prior art.
The alcohol that discharges by hydrolysis reaction in-situ silicon alkanisation can cause number of drawbacks in the further processing of resins, as quickening or the delay cross linking process.In addition, Silanization reaction requires the quite a long time and/or uses catalyzer and/or heating and optional measurement to be used to remove the alcohol and the excessive silane of formation.
In liquid or paste resin, the present invention comprises the methacrylic acid group and by the use of the silicon-dioxide of flame hydrolysis preparation, can mainly be that the sedimentation behavior of those fillers with coarse relatively particle size exists favorable influence to other fillers, even the sort of influence is not just worked immediately.
Embodiment
Embodiment
Comparative example 1:
The solution of methyl-ethyl-ketone peroxide in dimethyl phthalate 100 weight parts are undersaturated, that comprise cinnamic m-phthalic acid vibrin and 1 weight part 33% mixes by dissolver.Viscosity under 23 ℃ by rheometer measurement (here with the following example in the viscosity data measured summarize list in table 1).Then liquid is injected orthogonal with the paper tinsel that separates steel mould as lining, and 80 ℃ of heating 15 minutes under the seal-off pressures of 100 crust.During this period of time, component completely solidified and be configured as transparent thin slice.
Comparative example 2:
With the resin of the comparative example 1 of 100 weight parts by dissolver and 15 weight parts scribble trimethyl silyl group and by the flame hydrolysis preparation, its specific surface area is that 173 square metres, carbon content assay determination are that 3.4 weight %, its structure are mixed by the silicon-dioxide of mechanical alteration after handling.Viscosity is measured by the degassing brief in the low pressure cupboard down at 23 ℃.The pasty state composition that so obtains has tangible flow limitation, but still can sprawl.Add 33%MEK (methyl ethyl ketone) peroxide solutions of 1 weight % in addition, and in rectangular mould, heated under 80 ℃ 15 minutes.During this period of time, preparation completely solidified and from mould, shift out as translucent thin slice.
Embodiment 1 (prior art):
With 15 weight parts comprise the methacrylic acid group and by flame hydrolysis preparation and have a 160m
2The silicon-dioxide of the average particulate size of the specific surface area of/g and 12 nanometers and 5% carbon content comprises cinnamic m-phthalic acid vibrin by dissolver and 100 weight parts undersaturated and mixes.The blended air is removed by the degassing brief in the low pressure cupboard.Viscosity is passed through awl/plate rheometer measurement down at 23 ℃.Composition has flow limitation, but is easy to sprawl.Add 33%MEK (methyl ethyl ketone) peroxide solutions of 1 weight % in addition, and in rectangular mould, heated under 80 ℃ 15 minutes.During this period of time, composition completely solidified and from mould, shift out as translucent thin slice.
Comparative example 3 (prior art):
100 weight parts are undersaturated to be comprised in the cinnamic ethylene bromide base ester resin as joining as described in the embodiment 1 with 33%MEK (methyl ethyl ketone) peroxide solutions of 1 weight %; The mixture shaping is formed thin slice and curing.
Comparative example 4 (prior art):
With 100 weight parts undersaturated comprise cinnamic ethylene bromide base ester resin as described in example 1 above with 15 weight parts scribble trimethyl silyl group and by the flame hydrolysis preparation, have a 173m
2Specific surface area, its structure after handling, mixed by the silicon-dioxide of mechanical alteration.This composition is easy to flow.
Embodiment 2 (the present invention):
With 15 weight parts comprise the methacrylic acid group and by flame hydrolysis preparation, have a 160m
2Silicon-dioxide that the average particulate size of the specific surface area of/g, 12 nanometers and 5% carbon content, its structure are changed by mechanical post-treatments and 100 weight parts are undersaturated to comprise cinnamic ethylene bromide base mixed with resin.Do not have tangible flow limitation, composition can pour at an easy rate.It is mixed with 33%MEK (methyl ethyl ketone) peroxide solutions of 1 weight %, the degassing, shaping forms thin slice and is cured as described in example 1 above.
Comparative example 5 (prior art):
PMMA (polymethylmethacrylate) resin of 100 weight parts is dissolved in the monomeric methyl methacrylate, has composition:
A) monomer component of 20～95 weight %, it comprises
A1) (methyl) acrylic compound of 60～100 weight parts,
A2) multifunctional (methyl) acrylate of 0～40 weight part reaches
A3) the graft crosslinking agent of 0～10 weight part,
B) 5～80 weight % dissolve in polymkeric substance among the component A, and
C) free radical generating agent of 0.1～15 weight %, it has had low flow limitation,
The solidifying agent of this solution with 3 weight % mixed, and perfusion forms thin slice and at room temperature solidifies.After 15 hours, thin slice has cured fully.The remained on surface toughness.
Comparative example 6 (the present invention):
With 15 weight parts comprise trimethyl silyl group and by the preparation of trimethyl silyl flame hydrolysis, its specific surface area is 173m
2/ g, average particulate size are that 12 nanometers, carbon content are the PMMA mixed with resin of silicon-dioxide and the 100 weight part comparative examples 5 of 3.4 weight %.Preparation is compared the flow limitation with obvious increase with comparative example 5.Its solidifying agent with 3 weight % is mixed, and perfusion forms thin slice and at room temperature solidifies.The viscosity that remained on surface is slight.
Embodiment 3 (the present invention):
With the PMMA resin of 100 weight part comparative examples 5 rely on laboratory dissolver and 15 weight parts comprise the methacrylic acid group and prepare by flame hydrolysis, have a 160m
2The silicon-dioxide of/g specific surface area closely mixes, and it is slight increase that flow limitation is compared with potting resin (comparative example 5) not.Then the solidifying agent of mixture with 3 weight parts mixed, perfusion forms thin slice and at room temperature solidifies.After 16 hours, thin slice has cured fully.The surface does not have viscosity.
The experimental result summary
Table 1
The performance of uncured preparation
| Viscosity Pas, 5/s | Thixotropy index 2.5/5 | The above Pas of flow limitation | |
| Comparative example 1 | 1.34 | 1 | 0.2 |
| Comparative example 2 | 101.7 | 1.68 | 218 |
| Embodiment 1 | 12.9 | 1.42 | 7.6 |
| Comparative example 3 | 0.573 | 1 | 0.002 |
| Comparative example 4 | 95.7 | 1.77 | 258 |
| Embodiment 2 | 2.62 | 1.13 | 0.1 |
| Comparative example 5 | 8.24 | 1 | 40 |
| Comparative example 6 | 69 | 1.65 | 261 |
| Embodiment 3 | 23 | 1.26 | 65 |
The evaluation of table 1:
Even the selection high dosage comprises the methacrylic acid group and by the silicon-dioxide of flame hydrolysis preparation the influence of the viscosity of Plastic Resin composition and low flow limitation is had only quite little increase.This specific character is highly beneficial to further processing.
Table 2
The performance of solidified preparation
| Shore D hardness 10s/60s | Penetration hardness | Tensile strength Mpa | Tensile modulus Mpa | Modulus in flexure | ||
| Comparative example 1 | 78/76 | 87 | 47 | 2367 | 13853 | PE |
| Comparative example 2 | 84/83 | 106 | 48 | 3507 | 18893 | R8200 |
| Embodiment 1 | 84/83 | 118 | 55 | 4103 | 23764 | R7200 |
| Comparative example 3 | 86/85 | 73 | 70 | 4218 | 23764 | VE |
| Comparative example 4 | 85/84 | 119 | 50 | 4960 | 25213 | R8200 |
| Embodiment 2 | 85/84 | 121 | 43 | 6051 | 23540 | R7200 |
| Comparative example 5 | 82/80 | 101 | n.m. | n.m. | n.m. | MMA |
| Comparative example 6 | 83/81 | 110 | n.m. | n.m. | n.m. | R8200 |
| Embodiment 3 | 85/83 | 129 | n.m. | n.m. | n.m. | R7200 |
The evaluation of table 2:
Just as expected, silicon-dioxide causes hardness and modulus all to increase in crosslinked resin preparation.Although quite low BET surface-area is distinguished by basic more obviously effect with the silicon-dioxide of methacrylic acid group modification, it causes the tangible fragility of resin of embodiment 2.Those skilled in the art will recognize that here institute's accumulative potentiality and will reduce dosage or use more flexible base resin.
Claims (3)
1. the liquid hard plastics is characterized in that the silicon-dioxide that it comprises the pyrolysis method preparation of using the silane modified surface that contains the methacrylic acid group.
2. the liquid hard plastics of claim 1, the silicon-dioxide that it is characterized in that described pyrolysis method preparation is by structurally-modified.
3. strengthen the method for rigid plastics, it is characterized in that preparing uncrosslinked resin with the mixture of the silicon-dioxide of the pyrolysis method preparation of the silane modified surface that contains the methacrylic acid group.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/EP2002/007276 WO2004005393A1 (en) | 2002-07-02 | 2002-07-02 | Liquid duroplastics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1633467A CN1633467A (en) | 2005-06-29 |
| CN100575403C true CN100575403C (en) | 2009-12-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN02829252A Expired - Fee Related CN100575403C (en) | 2002-07-02 | 2002-07-02 | The liquid hard plastics |
Country Status (6)
| Country | Link |
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| EP (1) | EP1517949A1 (en) |
| JP (1) | JP2005531672A (en) |
| CN (1) | CN100575403C (en) |
| AU (1) | AU2002321158A1 (en) |
| TW (1) | TW200401798A (en) |
| WO (1) | WO2004005393A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7701550B2 (en) | 2004-08-19 | 2010-04-20 | Asml Netherlands B.V. | Lithographic apparatus and device manufacturing method |
| WO2006053632A2 (en) * | 2004-11-18 | 2006-05-26 | Degussa Gmbh | Hydrophobic silica and its use in silicone rubber |
| DE102007024099A1 (en) | 2007-05-22 | 2008-11-27 | Evonik Degussa Gmbh | adhesives |
| WO2013156337A1 (en) | 2012-04-20 | 2013-10-24 | Evonik Degussa Gmbh | Reinforced epoxy resin adhesive |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3328339A (en) * | 1963-08-28 | 1967-06-27 | Monsanto Co | Reinforced plastics containing base treated, calcined particulate fillers and organosilane coupling agents |
| ATE492607T1 (en) * | 2000-10-21 | 2011-01-15 | Evonik Degussa Gmbh | FUNCTIONALIZED SILICACIDS |
| EP1199337B1 (en) * | 2000-10-21 | 2011-01-19 | Evonik Degussa GmbH | Radiation curable lacquer systems |
| EP1199336B1 (en) * | 2000-10-21 | 2014-01-15 | Evonik Degussa GmbH | Functionalized, structure modified silicic acids |
-
2002
- 2002-07-02 CN CN02829252A patent/CN100575403C/en not_active Expired - Fee Related
- 2002-07-02 JP JP2004518475A patent/JP2005531672A/en not_active Withdrawn
- 2002-07-02 WO PCT/EP2002/007276 patent/WO2004005393A1/en not_active Application Discontinuation
- 2002-07-02 EP EP02754810A patent/EP1517949A1/en not_active Ceased
- 2002-07-02 AU AU2002321158A patent/AU2002321158A1/en not_active Abandoned
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Also Published As
| Publication number | Publication date |
|---|---|
| EP1517949A1 (en) | 2005-03-30 |
| TW200401798A (en) | 2004-02-01 |
| CN1633467A (en) | 2005-06-29 |
| AU2002321158A1 (en) | 2004-01-23 |
| JP2005531672A (en) | 2005-10-20 |
| WO2004005393A1 (en) | 2004-01-15 |
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