CN102585155A - PUA (polyurethane) reactive resin and preparation method thereof - Google Patents
PUA (polyurethane) reactive resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a PUA (polyurethane) reactive resin and a preparation method thereof. The PUA (polyurethane) reactive resin is prepared from a terminal hydroxyl dialkene oligomer, a diisocyanate compound, an optional polyhydric alcohol, and -OH containing (methyl) acrylate; and the obtained reactive resin comprises a dialkene oligomer soft segment and a diamino formate hard segment, and molecular chain terminal containing a (methyl) acyloxy group. The PUA reactive resin disclosed by the invention is based on the principle of stepwise polymerization of hydroxyl groups and isocyanate groups, has low water absorptivity and good water resistance, chemical resistance, storage capability and plastic adhesion by reasonably configuring the proportional relation among raw materials.
Description
Technical field
The present invention relates to the reaction resin field, especially relate to a kind of PUA reaction resin and preparation method thereof.
Background technology
The resin that contains carbon carbon unsaturated double-bond (C=C) is one type of reaction resin; The mode of this reaction resin available light or thermal initiation is reacted moulding; Can be used as the coating resin of photocuring, thermofixation, also can be used as the resin dedicated, of many uses of sticker and encapsulation or sealing.The reaction resin that contains the C=C group commonly used comprises unsaturated polyester, epoxy acrylic resin (PEA), polyurethane acrylic resin (PUA), polyester acrylic resin, polyoxyalkylene acrylate resin, acrylated WL 140 etc.These resins are convenient; The performance variable range is wide; The basic performance requriements that can satisfy general and normal condition; For example, can be used for Photocurable adhesive, printing-ink of photo-cured coating, the general applications of civilian decoration and protectiveness etc., these reaction resins are bases of present radiation curing technology and product.But for the purposes of being strict with is arranged more, as be used for bonding, the electronic product encapsulation etc. of plastic basis material, these resins can not satisfy performance requriements at aspects such as sticking power, water tolerance, erosion resistance chemical reagent.
In the existing reaction resin that contains the C=C group, Comparatively speaking PUA resin possess hydrophilic property is strong, softness; The advantage good, but existing P UA resin to the sticking power of polar substrates, for example polyester or the polyethers with terminal hydroxy group is the PUA of main raw material; Also there is poor adhesive force to non-polar plastic; Water-intake rate is high, and anti-strong chemical reagent and water tolerance are bad, and waiting of weathering resistance difference is not enough.
PUA type resin be the isocyanate groups that utilizes diisocyanate cpd (NCO) be bridge-jointing unit, with hydroxyl (OH) propenoate of group with contain-resin of OH is connected and prepares.In order to improve the performance of existing PUA type resin, make it more meet application requiring, need improve PUA type reaction resin.
At the Chinese patent publication number is in the patent of CN201010297425.5; " a kind of light-cured resin with low water absorption and preparation method thereof " disclosed; Wherein this light-cured resin is silane-modified hydroxy-terminated polybutadienes type polyurethane propenoate; Through both-end hydroxyl polyhutadiene oligopolymer and diisocyanate cpd are reacted, the end capped midbody of generation-NCO uses an end to be secondary amine then; The other end is secondary hydroxyl, contain the silicone compounds chain extension of a plurality of alkoxyl groups, will stay again at last-NCO with contain-acrylate reactions of OH group prepares.
Though the siloxane unit in the resulting molecular resin chain of above-mentioned patent has reduced the water-intake rate of resin; But the stability to hydrolysis of siloxane unit that contains a plurality of alkoxyl groups is bad, particularly under acid or alkali condition, even a spot of water; Even moisture all makes the siloxane groups generation hydrolysis of a plurality of alkoxyl groups easily; Deviate from alkoxyl group, generate the Si-O-Si structure, make resin gelization.This chemical property that contains the siloxane groups of a plurality of alkoxyl groups be the chemical fundamentals that siloxane compound is used as coupling agent, but for reaction resin, particularly the stability in storage to light-cured resin can cause serious problem.Therefore, this type light-cured resin of containing a plurality of oxyalkylsiloxane groups can not be used for the photocuring product of slant acidity or alkalescence.
In addition, because amido and isocyanate compound reactive activity are high, using an end to be secondary amine, when the other end was the silicone compounds chain extension of secondary hydroxyl, the controllability of reaction was bad, and resin viscosity is big, and is unfavorable to the use of product.
As far as PUA type reaction resin, also need further improve its poor adhesive force to non-polar plastic, water-intake rate is high, and anti-strong chemical reagent and water tolerance are bad, and waiting of weathering resistance difference is not enough.
Summary of the invention
The present invention aims to provide a kind of PUA type reaction resin and preparation method thereof, and PUA type reaction resin water-intake rate is high, water-fast and acidproof in the prior art, alkali resistance is bad to solve, to the problem of the poor adhesive force of plastics.
For realizing above-mentioned purpose; According to an aspect of the present invention; A kind of PUA type reaction resin is provided; PUA type reaction resin is terminal hydroxy group diolefine oligopolymer, diisocyanate cpd, optional polyvalent alcohol, contain-and (methyl) propenoate of OH is prepared from, and the reaction resin that makes comprises soft section of diolefine oligopolymer and hard section of double carbamate, and the molecule chain end that contains (methyl) acryloyl-oxy group.
Further, number sum >=8 of carbon atom in the saturated carbon chains of above-mentioned polyvalent alcohol (C), Sauerstoffatom (O) and/or sulphur atom (S) o'clock also comprise by saturated carbon chains formed soft section in soft section of prepared reaction resin.
Further, on average contain 1-5 soft section, 2-6 hard section and 2-4 (methyl) acryloyl-oxy group molecule chain end on the molecular chain of above-mentioned PUA type reaction resin.
Further, the mol ratio of above-mentioned polyvalent alcohol and terminal hydroxy group diolefine oligopolymer is 0～2: 1; In the diisocyanate cpd-NCO functional group and polyvalent alcohol and terminal hydroxy group diolefine oligopolymer in-mol ratio of OH functional group sum is 6/5～2/1.
Further, the number-average molecular weight of above-mentioned both-end hydroxyl diolefine oligopolymer is 800-6000g/mol, and perhaps OH value is 0.3～2.5mmol/g.
Further, above-mentioned terminal hydroxy group diolefine oligopolymer comprises the terminal hydroxy group diolefine oligopolymer that contains the itrile group group, and wherein the content of itrile group group is M, 0＜M≤22%, preferably, 5＜M≤22%.
Further, above-mentioned terminal hydroxy group diolefine oligopolymer comprises the terminal hydroxy group diolefine oligopolymer that contains phenyl group, and wherein the content of phenyl group is X, 0＜X≤22%, preferably, 0＜X≤18%.
Further, above-mentioned polyvalent alcohol is divalent alcohol and/or the trivalent alcohol that contains 2～20 carbon atoms, and the mol ratio of polyvalent alcohol and terminal hydroxy group diolefine oligopolymer is 1: 10～2: 1;
Further, when polyvalent alcohol was divalent alcohol and trivalent alcohol, the ratio of the molar weight of trivalent alcohol and divalent alcohol and terminal hydroxy group diolefine oligopolymer molar weight sum was R, 0＜R≤2.
Simultaneously,, a kind of preparation method of PUA type reaction resin is provided also, has may further comprise the steps: generated the preform of end group for-NCO with terminal hydroxy group diolefine oligopolymer, optional polyvalent alcohol and diisocyanate cpd reaction in another aspect of the present invention; With containing-(methyl) propenoate of OH and preform reaction generation PUA type reaction resin.
Further, above-mentioned preparation end group comprises for the step of the preform of-NCO, and the terminal hydroxy group diolefine oligopolymer behind the decompression dehydration is mixed the formation solution A with optional polyvalent alcohol and optional catalyzer heated and stirred; In solution A, add diisocyanate cpd, elevated temperature is not to being higher than 70 ℃ gradually, and reaction 1～2.5h obtains the preform of end group for-NCO; Perhaps diisocyanate cpd is mixed with optional polyvalent alcohol; Be not higher than 70 ℃ of following stirring reaction 0.5～2h in temperature; Form solution B; Add terminal hydroxy group diolefine oligopolymer and optional catalyzer behind the decompression dehydration, controlled temperature is not to being higher than 70 ℃ of stirring reaction 1～2.5h, obtains the preform of end group for-NCO;
Further; Above-mentioned usefulness contains-and (methyl) propenoate of OH and preform reaction generate PUA type reaction resin and comprise; In the preform of end group, add and contain-(methyl) propenoate of OH and optional thinner,, promptly get PUA type reaction resin at 50～70 ℃ of stirring reaction 1～3h for-NCO.
Beneficial effect of the present invention: the PUA type reaction resin that the application provided; Be based on progressively polymeric principle of oh group and isocyanate groups; Through reasonably disposing the proportionlity between raw material and the raw material; Formation has soft section of diolefine oligopolymer and hard section of double carbamate; And (methyl) acryloyl-oxy group is the PUA type reaction resin of molecule chain end, and this PUA type reaction resin has that water-intake rate is low, water-fast and acidproof, alkali resistance is good, stability in storage is good and the advantage good to the sticking power of plastics.
Embodiment
Need to prove that under the situation of not conflicting, embodiment and the characteristic among the embodiment among the application can make up each other.Specify the present invention below with reference to specific embodiment.
In a kind of typical embodiment of the present invention; A kind of PUA type reaction resin; Terminal hydroxy group diolefine oligopolymer, diisocyanate cpd, optional polyvalent alcohol and contain-(methyl) propenoate of OH is prepared from; The reaction resin that makes comprises hard section of soft section of diolefine oligopolymer and double carbamate, and (methyl) acryloyl-oxy group molecule chain end.
The polarity of above-mentioned double carbamate group is big, and Intermolecular Forces is strong, is the rigid chain segment on the molecular chain; And the polarity of chain of terminal hydroxy group oligopolymer is little; Second-order transition temperature is usually less than or near room temperature, segment is soft relatively, is the soft segment on the molecular resin chain.In order to describe the convenience of molecular structure, in the present invention double carbamate is called hard section, the diolefine oligopolymer is called soft section.
The PUA type reaction resin that the application provided is based on oh group and isocyanate groups step-reaction polymerization, generates the principle of urethane polymer (PU).Through reasonably selecting and dispose raw material, form with diolefine oligopolymer soft section and hard section of specific double carbamate, and the PUA type reaction resin of (methyl) acryloyl-oxy group molecule chain end.
Below provided the reaction formula of the main chemical reactions that is taken place between each feed composition in a kind of preparation process of PUA type reaction resin.In order to simplify this reaction formula, in following reaction formula,
Represent both-end hydroxyl diolefine oligopolymer, OCN-R-NCO represents diisocyanate cpd, and polyvalent alcohol is selected butyleneglycol for use,
Represent soft section, R '=-CH
3,-H,
Reaction formula is following:
Can find out by above-mentioned reaction formula, on average comprise two soft section, two (methyl) acryloyl-oxy group molecule chain ends (wherein for R " be (methyl) acryloyl-oxy group molecule chain end) and four double carbamate segments that form by vulcabond in the molecular chain of prepared PUA type reaction resin.Because employed butyleneglycol carbochain section is shorter relatively, so linking to each other through short butane segment, two double carbamates of intermediary form a hard section, this just makes and only contains three hard sections in the molecular chain of resulting PUA type reaction resin.
In the example that above-mentioned reaction formula provides; If the saturated divalent alcohol with number sum >=8 of C, S, O atom replaces butyleneglycol; At this moment; The molecular chain middle portion of resulting PUA type reaction resin product becomes the formed segment of saturated carbon chains by number sum >=8 of C, S, O atom, and these segmental two ends are connected with hard section an of double carbamate respectively, owing to be flexible unit by the formed segment of saturated carbon chains of number sum >=8 of C, S, O atom; At this moment; The molecular chain of prepared PUA type reaction resin will increase a flexible carbochain unit, and two double carbamates on both sides, soft segment unit are separated by flexible carbochain in the middle of being positioned at simultaneously, form two hard sections.
The divalent alcohol (above-mentioned reaction adopt be butyleneglycol) that replaces number sum＜8 of C, S, O atom in the saturated carbon chains with the divalent alcohol of number sum >=8 of C, S, O atom in the saturated carbon chains is when carrying out above-mentioned reaction; The molecular chain of prepared PUA type reaction resin becomes hard section (with two double carbamates that linked to each other by the formed soft section two ends of saturated carbon chains, with two double carbamates that link to each other with molecule chain end) that comprise 3 soft section (two diolefine oligopolymer soft section with by formed soft section of saturated carbon chains), 2 (methyl) acryloyl-oxy group molecule chain ends and 4 carbamates.
For the purpose of sake of clarity, when design and preparation PUA molecular resin, if the saturated carbon chains of employed polyvalent alcohol contains number sum >=8 o'clock of C and O and/or S atom, this saturated chain carbon will be calculated as soft section in the PUA resin.What is called contains the saturated carbon chains of C and O and/or S atom number sum >=8, is meant that C and O and/or S atom with saturated covalent linkage and the carbochain that directly is connected with linear mode, wherein can have ehter bond or thioether bond; When calculating the atom number of saturated carbon chains, each O of ehter bond on the carbochain or thioether bond or S atom all are calculated as an atom, are not counted in the atomicity of carbochain at the group of carbochain side group.For example, 1, the 8-ethohexadiol is the saturated carbon chains that 8 carbon atoms are arranged, and Tri Ethyleneglycol has six carbon atom and two O atoms, and tripropylene glycol also has the carbochain of six C atoms and two O atoms, all meets soft section definition.
Those skilled in the art are according to explanation of the present invention; Have the ability through reasonably combination raw materials, adjustment raw material order of addition(of ingredients), stepwise reaction and control the level of response in per stage; And use the identical or discrepant diisocyanate cpd of chemically reactive, can design, synthesize the PUA resin of different soft, hard hop count orders and molecular conformation.
Preferably, on average contain 1-5 soft section, 2-6 hard section and 2-4 (methyl) acryloyl-oxy group molecule chain end on the molecular chain of PUA type reaction resin of the present invention, the wherein soft section quantity employing aforesaid way with hard section calculates.
PUA type reaction resin in above-mentioned characteristic range, preparation easily, production technique is simple, and have that water-intake rate is lower, water-tolerant, storage characteristics, to the sticking power of plastics with to acid, the excellent in stability of alkali, the good characteristic of over-all properties.
The molecular chain of PUA type reaction resin provided by the present invention; Include but not limited to the linearity that following structural formula (1), (2), (3), (4) and (5) are represented or the molecular conformation of branching; In order to reduce the structure length, the hard section of
representative, soft section of
representative, A representative (methyl) acryloyl-oxy group in following structural formula (1), (2), (3), (4) and (5).
Soft for not requiring, hard section PUA resin (for example shown in the structural formula (5)) that particular sorted order arranged, or do not use the PUA resin of polyvalent alcohol; The simplest PUA molecular resin (for example shown in the structural formula (1)) that perhaps has only 2 hard sections, 2 (methyl) acryloyl-oxy groups and 1 soft section; Resin synthetic raw materials mode can make earlier-preform of NCO group end capping; And can be earlier with containing-(methyl) propenoate of OH and the reaction of excessive diisocyanate cpd, and then the mode that adds the reaction of both-end hydroxyl diolefine oligopolymer prepares.
Preferably, above-mentioned PUA type reaction resin prepares in the process, and the mol ratio of polyvalent alcohol and terminal hydroxy group diolefine oligopolymer is 0～2: 1; In the diisocyanate cpd-NCO functional group and polyvalent alcohol and terminal hydroxy group diolefine oligopolymer in-mol ratio of OH functional group sum is 6/5～2/1.Under this conditions of mixture ratios, favourable formation has soft section, hard section and the PUA type reacting resin of (methyl) acryloyl-oxy group molecule chain end quantity of specific quantity, and then promotes the over-all properties of prepared resin.
Terminal hydroxy group diolefine oligopolymer is one type of telechelic oligoner in the present invention, and two terminal hydroxy group are arranged.The preparation method of the terminal hydroxy group diolefine oligopolymer of the distant pawl type of this type has a lot; For example; Can use the method for oxyethane termination reaction then, again for example with the diolefine active anionic polymerization of bifunctional initiator initiation; Can cause diolefine radical polymerization with hydrogen peroxide, the method for the double-basis coupling termination reaction through terminal hydroxy group diolefine macromolecular radical prepares; Hydrogenant diolefine oligopolymer can carry out hydrogenation with terminal hydroxy group diolefine oligopolymer with palladium catalyst and appropriate reaction conditions and make.The micro chemical of terminal hydroxy group diolefine oligopolymer that different methods is prepared and hydrogenant terminal hydroxy group diolefine oligopolymer is different; For example 1; The chain structure after the ratio of 2 and 1,4 structure, the ratio of genial transconfiguration, the hydrogenation and the end of the chain are that hydroxyl of one-level or secondary etc. is different.PUA type reaction resin provided by the present invention; Can be according to the requirement of preparation method and required chemical structure; Select terminal hydroxy group diolefine oligopolymer and/or hydrogenant terminal hydroxy group diolefine oligopolymer for use, and the hydroxyl terminal in these oligomer chain can be primary hydroxyl or secondary hydroxyl.
Above-mentioned PUA type reaction resin prepares employed terminal hydroxy group diolefine oligopolymer in the process, includes but not limited to terminal hydroxy group TR 301, hydroxy-terminated polybutadienes hydrocarbon and hydrogenant terminal hydroxy group diolefine oligopolymer.The diolefine oligopolymer has that viscosity is low, good fluidity, water-fast, hydrophobic, anti-strong chemical reagent, molecular chain are soft, to characteristics such as the sticking power of non-polar plastic are good; Simultaneously diolefine low-grade polymer molecule chain end-the OH radical reaction is active high; Fast with isocyanate reaction; Also control easily, can effectively improve the performance of prepared PUA type reaction resin with the diolefine low-grade polymer as the raw material of PUA.
Preferably, it is 800g/mol～6000g/mol that above-mentioned terminal hydroxy group diolefine oligopolymer adopts number-average molecular weight, and perhaps OH value is at the terminal hydroxy group diolefine oligopolymer of 0.3mmol/g～2.5mmol/g.If the oligopolymer hydroxyl value is too big, the molecular weight of diolefine oligopolymer will be relatively low, in the PUA type resin of gained soft section shorter, and the carbamate hard segment content is bigger, and the water-intake rate of resin is higher, and water tolerance is outstanding; If hydroxyl value is too little, the molecular weight of diolefine oligopolymer is just bigger, and the resin viscosity of gained is bigger, and property is soft, and physical strength is relatively poor.More preferably; The number-average molecular weight of above-mentioned terminal hydroxy group diolefine oligopolymer is preferably 1400g/mol～6000g/mol; The hydroxyl value of perhaps above-mentioned terminal hydroxy group diolefine oligopolymer is preferably 0.3～1.3mmol/g; In this scope, the viscosity and the chemically reactive of terminal hydroxy group diolefine oligopolymer are suitable, and the over-all properties of resulting PUA type resin is also best.
In terminal hydroxy group diolefine oligopolymer of the present invention, can also contain an amount of itrile group group (CN); The adding of-CN group helps increasing the sticking power of resin to polar substrates, also helps the consistency that improves PUA type reaction resin of the present invention and other resin or compound.
The above-mentioned terminal hydroxy group diolefine oligopolymer that contains the itrile group group can be through similar terminal hydroxy group diolefine oligopolymer the method for radical polymerization, obtain with diolefine and acrylonitrile compolymer.The terminal hydroxy group diolefine oligopolymer that contains the itrile group group in the present invention; Include but not limited to the multipolymer of terminal hydroxy group butadiene hydrocarbon-vinyl cyanide, the multipolymer of terminal hydroxy group isoprene hydrocarbon-vinyl cyanide, perhaps the copolymerization that mixes diolefine and vinyl cyanide of the isoprene of terminal hydroxy group and divinyl.In the above-mentioned terminal hydroxy group diolefine oligopolymer that contains the itrile group group, the mass content of-CN group is M, 0＜M≤22%.Preferably, 5%＜M≤22%.In this scope, the viscosity of oligopolymer is suitable, can reach the mechanical property that improves final PUA resin; Improve the purpose with the consistency of other resin, if-too high levels of CN group, the water-absorbent of final PUA resin can increase; The viscosity of resin is big simultaneously, and color is dark, resin hardens.
Preferably, comprise the terminal hydroxy group diolefine oligopolymer that contains the CN group simultaneously in the above-mentioned terminal hydroxy group diolefine oligopolymer and do not contain-the terminal hydroxy group diolefine oligopolymer of CN group.Both are used, can control preferably-the CN group content, make its content not too high, the too high meeting of the content of-CN group makes polarity, water-intake rate and the viscosity of prepared PUA type resin increase resin hardens.More preferably, contain in the above-mentioned terminal hydroxy group diolefine oligopolymer-the terminal hydroxy group diolefine oligopolymer of CN group and not containing-mass ratio of the terminal hydroxy group diolefine oligopolymer of CN group is 0～5: 1.
In the molecular chain of terminal hydroxy group diolefine oligopolymer of the present invention, can also contain an amount of phenyl ring group (Ph); PUA molecular resin chain adding-Ph group helps increasing the mechanical strength of PUA resin and to the sticking power of plastic basis material, also help improving PUA thermotolerance and with the consistency of other resin or compound.
The terminal hydroxy group diolefine oligopolymer of above-mentioned containing-Ph group can be that material copolymerization obtains with diolefine and vinylbenzene through the preparation method of similar above-mentioned terminal hydroxy group diolefine oligopolymer.Contain in the present invention-the terminal hydroxy group diolefine oligopolymer of Ph group; Include but not limited to terminal hydroxy group butadiene hydrocarbon-cinnamic multipolymer, terminal hydroxy group isoprene hydrocarbon-cinnamic multipolymer, perhaps the isoprene of terminal hydroxy group and divinyl mixes diolefine and cinnamic copolymerization.In the terminal hydroxy group diolefine oligopolymer of above-mentioned containing-Ph group, the mass content X of-Ph group can be in 0＜X≤25% scope, preferably, and 0＜X≤18%.In this scope, the viscosity of oligopolymer is suitable, can reach the mechanical property that improves the PUA resin, improves the purpose with the consistency of other resin, if-too high levels of Ph group, will make the PUA resin hardens, simultaneously the transparency and light fastness aging decline.
In a kind of concrete embodiment of the present invention, comprise simultaneously in the above-mentioned terminal hydroxy group diolefine oligopolymer containing-the terminal hydroxy group diolefine oligopolymer of Ph group and not containing-the terminal hydroxy group diolefine oligopolymer of Ph group.Both are used, can more easily regulate-content of Ph group, the content of-Ph group is too high, and the viscosity of prepared PUA type resin is increased, resin hardens, the transparency and light fastness aging decline.More preferably, contain in the above-mentioned terminal hydroxy group diolefine oligopolymer-the terminal hydroxy group diolefine oligopolymer of Ph group and not containing-mass ratio of the terminal hydroxy group diolefine oligopolymer of Ph group is 0～5: 1.
In a kind of concrete embodiment of the present invention, also add polyvalent alcohol in the preparation of above-mentioned PUA type reaction resin, two～tetravalent alcohol for example, preferably, polyvalent alcohol is selected from divalent alcohol and/or the trivalent alcohol that contains 2～20 carbon atoms.This polyvalent alcohol is except that containing 2～20 the carbon atom, can also contain S and/or not belong to the O atom of hydroxyl.
In PUA type reaction resin of the present invention; If add an amount of small molecules polyvalent alcohol; Can regulate on the prepared PUA type reaction resin molecular chain soft, hard section content and ratio through the combination of polyvalent alcohol and terminal hydroxy group diolefine oligopolymer; Strengthen the reactive force between the molecular resin, improve the mechanical property of prepared PUA type reaction resin, and improve bonding force polar substrates; With the trivalent alcohol or the polyvalent alcohol of high functionality more, can obtain the PUA molecular resin chain of branching form, and then obtain the PUA resin of excellent combination property.
The mol ratio of preferably, in the present invention employed polyvalent alcohol and terminal hydroxy group diolefine oligopolymer is 0～2: 1.In actual mechanical process; Can adjust according to the performance requriements of the molecular weight of terminal hydroxy group diolefine oligopolymer and prepared PUA type reaction resin: if the molecular weight of employed terminal hydroxy group diolefine oligopolymer is little; The viscosity of perhaps required PUA type reaction resin is little; Then the consumption of polyvalent alcohol can reduce in right amount, does not even use.If the molecular weight of employed terminal hydroxy group diolefine oligopolymer is big, the viscosity of perhaps required PUA type reaction resin is big, and then the consumption of polyvalent alcohol just needs an amount of increasing, and makes the mol ratio of polyvalent alcohol and terminal hydroxy group diolefine oligopolymer reach 2.If but the consumption of polyvalent alcohol is too much, such as the mol ratio of polyvalent alcohol and terminal hydroxy group diolefine oligopolymer greater than 2, then hard section of the PUA resin of gained too many, it is big that water-intake rate becomes, viscosity is excessive.Preferably, the mol ratio of polyvalent alcohol and terminal hydroxy group diolefine oligopolymer is 1: 10～2: 1.
Polyvalent alcohol can adopt divalent alcohol or trivalent alcohol separately in the present invention, also can divalent alcohol and trivalent alcohol be used.When using divalent alcohol; Diatomic alcohol compounds and di-isocyanate reaction, what obtain is the resin of linear structure, when using trivalent alcohol; Trivalent alcohol and di-isocyanate reaction; Can obtain the resin of one or many branching, the degree of branching of molecule and terminal number are relevant with functional group's proportioning of polyreaction, and be also relevant with the level of response of functional group.In theory, if only contain a trivalent alcohol unit on a molecular resin, promptly a molecular resin branching once, molecular resin has three end groups; If molecular resin contains two trivalent alcohols, then molecular resin branching twice, and then molecular resin has four end groups.The end group of reaction resin of the present invention is a reactive group, and end group is many more, and then the activity of resin is high more, but end group is many more, and then the content of the hard section of double carbamate is also many more in the resin, and the viscosity of resin is also big more.Though the resin with synthetic four chain ends of tetravalent alcohol is simpler in theory, the polarity of small molecules tetravalent alcohol is big, and poor with the consistency of terminal hydroxy group diolefine oligopolymer, solvability is little.So preferably adopt divalent alcohol and trivalent alcohol in the present invention.
Preferably, above-mentioned polyvalent alcohol can comprise divalent alcohol and trivalent alcohol simultaneously, and wherein the mol ratio of divalent alcohol and terminal hydroxy group diolefine oligopolymer is 0～2: 1, and the ratio of the integral molar quantity of the molar weight of trivalent alcohol and divalent alcohol and terminal hydroxy group diolefine oligopolymer is 0～2: 1.The mol ratio of divalent alcohol, trivalent alcohol and terminal hydroxy group diolefine oligopolymer is controlled in the above-mentioned scope; Help forming soft section of diolefine oligopolymer in each molecule and be 1-5,2-6 of the hard section of double carbamate, (methyl) acryloyl-oxy group molecule chain end 2-4 PUA type reaction resin, and then obtain good comprehensive properties PUA resin type reaction resin.
Optional in the present invention divalent alcohol includes but not limited to one or more in terepthaloyl moietie, Ucar 35, butyleneglycol, glycol ether, pentanediol, NSC 6366, pinakon, cyclohexanediol, heptanediol, ethohexadiol, dihydroxymethyl hexalin, glycol ether, tripropylene glycol, sulfo-glycol ether, Hydrogenated Bisphenol A 99, the diethoxy dihydroxyphenyl propane.Preferred carbon atom is at 2～20 binary primary alconol.Optional in the present invention trivalent alcohol includes but not limited in USP Kosher, TriMethylolPropane(TMP), ethoxylated trimethylolpropane and the propenoxylated TriMethylolPropane(TMP) one or more.The all preferred primary alconol of divalent alcohol and trivalent alcohol, the chemical reactivity of primary alconol and isocyanic ester is higher, helps the resin building-up reactions.
In a kind of embodiment of the present invention, the diisocyanate cpd for preparing above-mentioned PUA type reaction resin is aliphatic diisocyanate chemical combination or aromatic diisocyanate cpd.Particularly, diisocyanate cpd includes but not limited to tolylene diisocyanateization (TDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), YLENE alkane two isocyanic acids (MDI) and hydrogenation TDI, hydrogenation MD etc. in the present invention.
Can select the type of employed diisocyanate cpd according to the performance of required PUA type reaction resin.For example, the high reaction resin of intensity can be selected aromatic TDI and MDI for use if desired; Yellowing resistance is good if desired, and the reaction resin that viscosity is less can be selected aliphatic IPDI, HDI and hydrogenation TDI, hydrogenation MD for use.
In the process of preparation PUA type reaction resin of the present invention; In the diisocyanate cpd-molecular weight of the mol ratio decision resin of total-OH functional group in NCO functional group and polyvalent alcohol and the terminal hydroxy group diolefine oligopolymer; Also influence the viscosity of resin; Both proportionings are more near equal proportion, and the molecular weight of resin is high more, and viscosity is big more.To the reaction resin of linear structure, diisocyanate cpd-NCO group number manys two than total-OH group number of diolefine and polyvalent alcohol; Resin to three chain ends; Diisocyanate cpd-the NCO group Duos three than-OH group; Similarly; The resin that contains four chain ends, diisocyanate cpd-the NCO group Duos four than-OH group, and additional-NCO group is used to link and contains-(methyl) propenoate of OH group.Preferably, diisocyanate cpd-mol ratio of total-OH group of NCO functional group and polyvalent alcohol and terminal hydroxy group diolefine oligopolymer is 6: 5～2: 1.
In a kind of embodiment of the present invention; Be used for end group-NCO radical reaction with preform; (methyl) propenoate of the containing of preparation PUA type reaction resin-OH group includes but not limited to Rocryl 400 (HEMA), Rocryl 410 (HPMA), Hydroxyethyl acrylate (HEA) and Propylene glycol monoacrylate (HPA).Their consumption if can guarantee with the work in-process resin-NCO group total overall reaction finishes.
A kind of preparation method of PUA type reaction resin also is provided in the present invention, has may further comprise the steps: generated the preform of end group for-NCO with terminal hydroxy group diolefine oligopolymer, polyvalent alcohol and diisocyanate cpd reaction; With containing-(methyl) propenoate of OH and preform reaction generation sold resin.
Preferably; In the method for above-mentioned PUA type reaction resin; The preparation end group comprises for a kind of concrete steps of the preform of-NCO: the terminal hydroxy group diolefine oligopolymer behind the decompression dehydration is mixed the formation solution A with optional polyvalent alcohol and optional catalyzer heated and stirred; In solution A, add diisocyanate cpd, elevated temperature is not to being higher than 70 ℃ gradually, and reaction 1～2.5h obtains the preform of end group for-NCO.
In the process of this PUA type reaction resin of preparation; Because the reaction of hydroxyl and isocyanate groups almost is irreversible; In a single day reaction between the functional group has just formed and has been fixedly coupled order, so; Obtain specific soft, the hard section molecular chain of mode in succession, the raw material that reacts will add sequentially.The chemically reactive of the two-NCO reactive group of vulcabond is relevant with the group that is joined; For example the active difference of two-NCO reactive group is very big in tolylene diisocyanate (TDI) and the two different Buddhist diketone vulcabond (IPDI); Can utilize the order of addition(of ingredients) of this chemically active difference and raw material; Make soft, hard section to connect, the PUA molecule of specific soft, hard section sequence is arranged with preparation according to certain arrangement mode.
With reference to aforesaid PUA resin reaction formula; If with butyleneglycol and vulcabond reaction earlier; And then the reaction of adding terminal hydroxy group diolefine oligopolymer generates the end capped preform of NCO; Add at last and contain-feed way of (methyl) propenoate of OH; Because vulcabond is excessive in the reaction of butyleneglycol and vulcabond, the possibility that forms the polymer of butyleneglycol and vulcabond just significantly reduces, and most product is that the two ends of butyleneglycol connect upward isocyanic ester; The terminal hydroxy group diolefine oligopolymer that adds subsequently will with remaining di-isocyanate reaction in isocyanic ester on the two ends of butyleneglycol and the reaction system, maximize making like the represented molecule chain end that comprises two soft section, two methacryloxies groups of preceding formula and the product content of three hard segment structures.
In the preparation process of aforementioned PUA type reaction resin; Step-reaction polymerization is between hydroxyl and isocyanic ester, to carry out; So the reaction of various ways can take place between raw material and the raw material, and therefore, the molecular weight of reaction product and chemical constitution are not single; Promptly except the represented molecular structure of following formula; The molecule that also has the part resin is formed by soft section of diolefine oligopolymer and di-isocyanate reaction fully, also have a spot of molecule and formed by butyleneglycol and two di-isocyanate reactions fully, but the represented product structure of above-mentioned reaction formula is the maximum component of content in the reaction product.Carrying out molecular chain structure when design of PUA type reaction resin, is pairing resin structure with the product structure of this maximum distribution.The detailed knowledge of relevant step-reaction polymerization and reaction product can be referring to the books of polymer chemistry.
For branched structure and the viscosity of controlling resin; When using the performance of optional polyvalent alcohol adjustment PUA, preferably, let polyvalent alcohol react with diisocyanate cpd earlier; And then add terminal hydroxy group diolefine oligopolymer and further react, generate end group and be-preform of NCO.Such feed way; Since when polyvalent alcohol reacts with diisocyanate cpd earlier-the NCO group is excessive; Can suppress the polymerization of polyvalent alcohol and diisocyanate cpd, and the structure of main generation-NCO group end capping, after adding terminal hydroxy group diolefine oligopolymer; Polyvalent alcohol just can be distributed on the molecular resin chain dispersedly, generates controlled branched structure.
Preferably; In the method for above-mentioned PUA type reaction resin, the preparation end group comprises for a kind of concrete steps of the preform of-NCO: diisocyanate cpd is mixed with optional polyvalent alcohol, and temperature is not higher than 70 ℃ of following stirring reaction 0.5～2h; Form solution B; In solution B, add terminal hydroxy group diolefine oligopolymer and optional catalyzer behind the decompression dehydration, controlled temperature is not to being higher than 70 ℃ of stirring reaction 1～2.5h, obtains the preform of end group for-NCO.
Preferably; In the above-mentioned method for preparing PUA type reaction resin; A kind of usefulness contains-and (methyl) propenoate of OH and preform reaction generate PUA type reaction resin and comprise: in the preform of end group, add and contain-(methyl) propenoate of OH and optional thinner for-NCO; At 50～70 ℃ of stirring reaction 1～3h, promptly get PUA type reaction resin.The adding of thinner mainly is the viscosity that is used to reduce PUA type reaction resin.Thinner can contain in adding-(methyl) propenoate of OH before, perhaps after forming PUA type reaction resin, add.
Optional in the present invention catalyzer is compounds such as organometallic compound or organic amine.For example: dibutyl tin dilaurate, dibutyltin diacetate, stannous octoate, naphthenate, triethylamine, Tributylamine, triethylenediamine etc.
Optional in the present invention thinner comprises that lipid, ketone, ethers organic cpds, particularly carbonatoms are at this type organic solvent more than 4.Preferably to be not less than (methyl) acrylate ester of 4 alkyl alcohol be solvent to (methyl) esters of acrylic acid, particularly carbonatoms, for example: (methyl) Bing Xisuandingzhi, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid 12 alkyl esters; (methyl) IBOA etc.Simultaneously, preferred carbonatoms is greater than 6 divalent alcohol or two (methyl) propenoate or three (methyl) propenoate of trivalent alcohol, for example: pinakon double methacrylate, trimethylolpropane tris (methyl) propenoate etc.These (methyl) propenoate just can be removed and directly use as reactive thinner.Preferably, the consumption of thinner is the 0-25% of resin quality.
Preferably, the number-average molecular weight of PUA type reaction resin provided by the present invention is 1600g/mol-20000g/mol, and the viscosity of resin is advisable at 6Pa.S-300Pa.S.The molecular weight of resin is too small, and the relative content of reactive group is high, though active big, the volumetric shrinkage of curing reaction is big, and the degree of crosslinking of product is excessive, and performance is not good.If the molecular weight of resin is excessive, such as greater than 20000g/mol, the viscosity of resin is big, and the relative content of reactive functional groups is little, and the solidified degree of crosslinking is too small, and product feels like jelly, and performance is not good yet.The viscosity of resin is relevant with the molecular weight size on the one hand, and also relevant with the amount of diluent of adding, thinner strengthens, and the viscosity of resin is little, but the performance of resin can not give full play to, and the solidified volumetric shrinkage is big, and the smell of resin becomes greatly, and activity also possibly diminish; If without thinner, the viscosity of resin maybe be excessive, for example greater than 300Pa.S, is unfavorable for using.
Below will combine specific embodiment 1-14 and Comparative Examples 1-2 to further specify the beneficial effect of PUA type reaction resin provided by the present invention.
Embodiment 1:
Will be through terminal hydroxy group TR 301 (hydroxyl value 1.9mmol/g, number-average molecular weight the is 1000g/mol) 1000g of 110 ℃ of decompression dehydration 1h, diethoxy dihydroxyphenyl propane 632g and 1g stannous octoate are in 40 ℃ of stirrings, mixing; Add TDI 695g; Temperature of reaction progressively rises, and controlled temperature is no more than 70 ℃, adds Rocryl 400 270g and 250g NSC 20956 behind the reaction 2h; In 50-65 ℃ of stirring reaction 2.5h discharging, make PUA type reaction resin 1.
The number-average molecular weight of resin (diluent free, GPC, PS standard): 2000g/mol, resin viscosity (30 ℃): 10Pa.S.
Embodiment 2:
With 134g TriMethylolPropane(TMP) and 845g HDI reaction 2h, controlled temperature is no more than 70 ℃, adds terminal hydroxy group TR 301 (the hydroxyl value 1.9mmol/g that handles through 110 ℃ of decompression dehydrations; Number-average molecular weight 1000g/mol) 2500g and 2g stannous octoate, temperature progressively rises, and controlled temperature is no more than 70 ℃; Add Rocryl 400 270g behind the reaction 2.5h; Behind 50-65 ℃ of stirring reaction 3h, add the 500g Isooctyl acrylate monomer, the back discharging that stirs makes PUA type reaction resin 2.
Resin number-average molecular weight (diluent free, GPC, PS standard): 8000g/mol, resin viscosity (30 ℃): 120Pa.S.
Embodiment 3:
28 Hydroxyethyl acrylates are mixed at normal temperature with 42g HDI, and stirring reaction 2h, controlled temperature are no more than 60 ℃; Then at 400g terminal hydroxy group butadiene hydrocarbon-acrylonitrile copolymer (hydroxyl value 0.49mmol/g ,-CN mass percent 1%, molecular weight 2000g/mol) and 80g hydroxy-terminated polybutadienes hydrocarbon (the hydroxyl value 0.49mmol/g of 40 ℃ of addings through the decompression dehydration drying treatment; Number-average molecular weight～4000) and the 0.1g dibutyl tin dilaurate; Stirring reaction 3h, temperature progressively rises, and controlled temperature is no more than 75 ℃; Discharging after adding 70g butylacetate stirs makes PUA type reaction resin 3.
Resin number-average molecular weight (diluent free, GPC, PS standard): 4000g/mol, resin viscosity (30 ℃): 70Pa.S.
Embodiment 4:
To pass through 1000g terminal hydroxy group TR 301 hydrocarbon (the hydroxyl value 0.95mmol/g of decompression dehydration drying treatment; Number-average molecular weight 2000g/mol) and 60g terepthaloyl moietie, 1g dibutyl tin dilaurate 40 ℃ of stirrings, mix the back and add IPDI 450g; Temperature of reaction progressively rises, and controlled temperature is no more than 70 ℃, adds Propylene glycol monoacrylate 130g behind the reaction 1h; In 50-65 ℃ of stirring reaction 1.5h discharging, make PUA type reaction resin 4.
Resin number-average molecular weight (GPC, PS standard): 3500g/mol, resin viscosity (30 ℃): 200Pa.S.
Embodiment 5:
With 13g TriMethylolPropane(TMP) and 88g HDI, be no more than 70 ℃ of following stirring reaction 1h in temperature, add 530g terminal hydroxy group butadiene hydrocarbon-acrylonitrile copolymer (hydroxyl value 0.5mmol/g then through the decompression dehydration drying treatment;-CN mass percent 22%, molecular weight 2000g/mol) and 270g hydroxy-terminated polybutadienes hydrocarbon (hydroxyl value 0.49mmol/g, number-average molecular weight～4000), 6g sulfo-glycol ether, 1g triethylenediamine; Temperature of reaction progressively rises; Controlled temperature is no more than under 70 ℃, and stirring reaction 1h adds Rocryl 410 45g and 150g NSC 20956; In 50-65 ℃ of stirring reaction 2.5h discharging, make PUA type reaction resin 5.
Resin number-average molecular weight (diluent free, GPC, PS standard): 20000g/mol, resin viscosity (30 ℃): 300Pa.S.
Embodiment 6:
Triethoxy TriMethylolPropane(TMP) 26g and 115g hydrogenation TDI, stirring reaction 1h, controlled temperature are no more than 70 ℃; Adding will be passed through 165g hydroxy-terminated polybutadienes hydrocarbon (hydroxyl value 2.46mmol/g, number-average molecular weight 800g/mol), 166g terminal hydroxy group butadiene hydrocarbon-styrol copolymer (hydroxyl value 1.2mmol, the phenyl ring mass percent 1% of decompression dehydration drying treatment; Molecular weight 1500g/mol) and the 1g dibutyl tin dilaurate; Temperature progressively rises, and controlled temperature is no more than 70 ℃, adds Hydroxyethyl acrylate 35g and 100g Viscoat 295 behind the reaction 2.5h; In 60-70 ℃ of stirring reaction 1h discharging, make PUA type reaction resin 6.
Resin number-average molecular weight (diluent free, GPC, PS standard): 4500g/mol, resin viscosity (30 ℃): 90Pa.S.
Embodiment 7:
To pass through hydroxy-terminated polybutadienes hydrocarbon (the hydroxyl value 0.3mmol/g of decompression dehydration drying treatment; Number-average molecular weight 6000g/mol) 600g, 12 carbon glycol 10g and 1g triethylamine add 55g hydrogenation MDI in 40 ℃ of stirrings, mixing back; Temperature of reaction progressively rises, and controlled temperature is no more than 70 ℃, adds Hydroxyethyl acrylate 27g and 70g pinakon double methacrylate behind the reaction 1.5h; In 50-65 ℃ of stirring reaction 2h discharging, make PUA type reaction resin 3.
Resin number-average molecular weight (diluent free, GPC, PS standard): 4000g/mol, resin viscosity (30 ℃): 200Pa.S.
Embodiment 8:
Will be through 370g hydroxy-terminated polybutadienes hydrocarbon (hydroxyl value 2.46mmol/g, number-average molecular weight 800g/mol), 6g sulfo-glycol ether, 2g stannous octoate and the 138g IPDI of 110 ℃ of decompression dehydration 1h, stirring reaction; Controlled temperature is no more than 70 ℃; Add Rocryl 410 26g behind the reaction 2.5h, behind 50-65 ℃ of stirring reaction 3h, add the 180g Isooctyl methacrylate; Discharging after stirring makes PUA type reaction resin 8.
Resin number-average molecular weight (diluent free, GPC, PS standard): 6000g/mol, resin viscosity (30 ℃): 30Pa.S..
Embodiment 9:
Will be through hydrogenation terminal hydroxy group TR 301 (hydroxyl value 1.9mmol/g, the number-average molecular weight 1000g/mol) 100g of 110 ℃ of decompression dehydration 1h, tripropylene glycol 19g heats, stirs into homogeneous solution; Add IPDI70g after adding the 2g stannous octoate, temperature of reaction progressively rises, and controlled temperature is no more than 70 ℃; Add Rocryl 410 26g behind the reaction 2h, behind 60-70 ℃ of stirring reaction 1h, add the 50g Isooctyl acrylate monomer; Discharging after stirring makes PUA type reaction resin 9.
Resin number-average molecular weight (diluent free, GPC, PS standard): 8000g/mol, resin viscosity (30 ℃): 6Pa.S..
Embodiment 10:
With 134g TriMethylolPropane(TMP) and 670g IPDI reaction 0.5h; Controlled temperature is no more than 70 ℃, adds terminal hydroxy group TR 301 (hydroxyl value 1.9mmol/g, number-average molecular weight 1000g/mol) 450g, 3g terepthaloyl moietie and the 2g stannous octoate handled through 110 ℃ of decompression dehydrations; Temperature progressively rises; Controlled temperature is no more than 70 ℃, adds Rocryl 400 280g behind the reaction 2.5h, behind 50-65 ℃ of stirring reaction 2h, adds the 300g Isooctyl acrylate monomer; Discharging after stirring makes PUA type reaction resin 10.
Resin number-average molecular weight (diluent free, GPC, PS standard): 3500g/mol, resin viscosity (30 ℃): 150Pa.S..
Embodiment 11:
With 500g terminal hydroxy group butadiene hydrocarbon-acrylonitrile copolymer (the hydroxyl value 0.4mmol/g that adds through the decompression dehydration drying treatment;-CN mass percent 5%; Molecular weight 8000g/mol) and 12g HDI be no more than 70 ℃ of following stirring reaction 2.5h in temperature, add Rocryl 400 12g, behind 50-65 ℃ of stirring reaction 3h, add the 100g Isooctyl methacrylate; Discharging after stirring makes PUA type reaction resin 11.
Resin number-average molecular weight (diluent free GPC, PS standard): 9000g/mol, resin viscosity (30 ℃): 180Pa.S..
Embodiment 12:
With 300g terminal hydroxy group butadiene hydrocarbon-styrol copolymer (the hydroxyl value 0.6mmol/g that adds through the decompression dehydration drying treatment; Phenyl mass percent 18%; Molecular weight 2000g/mol), 4g TriMethylolPropane(TMP), 0.2g triethylenediamine and 32g TDI are no more than 70 ℃ of following stirring reaction 2.5h in temperature, adding Rocryl 400 40g, adding 70g Isooctyl acrylate monomer behind 50-65 ℃ of stirring reaction 3h; The discharging discharging makes PUA type reaction resin 12 after stirring.
Resin number-average molecular weight (GPC, PS standard): 8000g/mol, resin viscosity (30 ℃): 90Pa.S..
Embodiment 13:
With the 500g terminal hydroxy group isoprene hydrocarbon-styrol copolymer (hydroxyl value 0.8mmol/g, phenyl mass percent 10%, molecular weight 2500g/mol) and 100g terminal hydroxy group TR 301 hydrocarbon (the hydroxyl value 0.49mmol/g that add through the decompression dehydration drying treatment; Number-average molecular weight～4000), 0.5g triethylenediamine and 80g TDI temperature of reaction progressively rise, controlled temperature is no more than under 70 ℃; Stirring reaction 1h; Be no more than 70 ℃ of following stirring reaction 2.5h in temperature, add Rocryl 400 13g
Resin number-average molecular weight (GPC, PS standard): 3800g/mol, resin viscosity (30 ℃): 200Pa.S..
Embodiment 14:
With the 32g polyethers pentavalent alcohol (Dow chemical formula, trade mark Voranol 520, the hydroxyl value 9.3mmol/g that add through the decompression dehydration drying treatment; Molecular weight 550g/mol), 110g TDI is no more than 70 ℃ of following stirring reaction 2h in temperature, adds 1200g terminal hydroxy group butadiene hydrocarbon-acrylonitrile copolymer (hydroxyl value 0.5mmol/g;-CN mass percent 22%, molecular weight 2500), the 0.8g triethylenediamine, temperature of reaction progressively rises; Controlled temperature is no more than under 70 ℃, and stirring reaction 2h adds Rocryl 400 48g; Behind 50-60 ℃ of stirring reaction 1.5h, add the 300g N-BUTYL ACETATE, the back discharging discharging that stirs makes PUA type reaction resin 14.
Resin number-average molecular weight (GPC, PS standard): 22000g/mol, resin viscosity (50 ℃): 300Pa.S.
Comparative Examples 1:
Raw material: polycaprolactone divalent alcohol (hydroxyl value 2mmol/g, number-average molecular weight～1000) 100g; Dibutyl tin dilaurate 0.12g; IPDI 45g; Hydroxyethyl acrylate 23g.
Will be through the polycaprolactone divalent alcohol of 110 ℃ of decompression dehydration 1h; Dibutyl tin dilaurate adds IPDI in 50 ℃ of stirrings, mixing, and temperature of reaction progressively rises; Controlled temperature is no more than 70 ℃; Add Hydroxyethyl acrylate behind the reaction 1h,, make contrast PUA type reaction resin 1 in 50-65 ℃ of stirring reaction 2h discharging.
The number-average molecular weight (GPC, PS standard) of contrast PUA type reaction resin 1: 1800g/mo4, resin viscosity (50 ℃): 100Pa.S..
Comparative Examples 2:
Raw material: THF homopolymer divalent alcohol (hydroxyl value 2mmol/g, number-average molecular weight～1000) 100g; Dibutyl tin dilaurate 0.12g; IPDI 45g; Rocryl 400 26g
Will be through the THF homopolymer divalent alcohol of 110 ℃ of decompression dehydration 1h; Dibutyl tin dilaurate adds IPDI in 50 ℃ of stirrings, mixing, and temperature of reaction progressively rises; Controlled temperature is no more than 70 ℃; Add Rocryl 400 behind the reaction 1h,, make contrast PUA type reaction resin 2 in 50-65 ℃ of stirring reaction 2h discharging.
The number-average molecular weight (GPC, PS standard) of contrast PUA type reaction resin 2: 1800g/mol, resin viscosity (30 ℃): 120Pa.S..
For the ease of data and protection scope of the present invention among embodiment 1-14 and the Comparative Examples 1-2 are linked together, existing individual features with embodiment 1-14 and Comparative Examples 1-2 is summarized in the following table 1.
The corresponding structure characteristic comprises in the table 1:
A hurdle PB, PI, PB-CN, PI-CN, PB-St and PI-St represent hydroxy-terminated polybutadienes, terminal hydroxy group TR 301 respectively; Contain the CN group hydroxy-terminated polybutadienes, contain the terminal hydroxy group isoprene of CN group; Contain the hydroxy-terminated polybutadienes and the both-end hydroxyl isoprene that contains the Ph group of Ph group, the numerical value in the bracket is the hydroxyl value (mmol/g) of resin;
B hurdle 2 and 3 is represented binary and trivalent alcohol, C respectively
nO
mS
lMiddle n represents carbonatoms, the m represention oxygen atom number of polyvalent alcohol, and 1 represents the sulphur atom number;
The C hurdle is the molar ratio between polyvalent alcohol, terminal hydroxy group diolefine oligopolymer and the vulcabond; When wherein polyvalent alcohol comprises divalent alcohol and trivalent alcohol simultaneously, adopt the mode of (trivalent alcohol mole number+divalent alcohol mole number)/diolefine oligopolymer/vulcabond to represent;
D representes on the hurdle to contain the content of itrile group in the terminal hydroxy group diolefine oligopolymer of itrile group group or phenyl group or phenyl group, and the terminal hydroxy group diolefine oligopolymer and the quality ratio that does not contain the terminal hydroxy group diolefine oligopolymer of itrile group or phenyl group that contain itrile group or phenyl group;
E representes on the hurdle in the prepared PUA type reaction resin soft section, hard section, the number of (methyl) acryloyl-oxy group molecule chain end.
Table 1
The resin property test:
Specimen preparation: get institute's synthetic reaction resin 100g among embodiment 1-14 and the Comparative Examples 1-2; Add 20g Bing Xisuandingzhi and 2g light trigger 1173 and stir, obtain mixture, mixture is placed between the two-layer PET film; The spacing of two-layer PET film is 0.03mm; With the high voltage mercury lamp radiation 50s of 1000w, lamp is apart from 30cm, the sample 1-16 after must solidifying.
Evaluation method
The viscosity measurement of resin; Adopt rotary viscometer to test embodiment 1-14 and the prepared reaction resin of Comparative Examples 1-2, measuring result is as shown in table 2.
The water-intake rate of resin is measured: above-mentioned sample 1-16 is put into the velocity of variation of weigh behind 100 ℃ the water 1h, measuring result such as table 2.
The hydrolysis stability measurement of resin: add the water of mass ratio 5% and 1% phosphoric acid (mass concentration 85%) in the reaction resin that embodiment 1-14 and Comparative Examples 1-2 is prepared; In 60 ℃ baking oven, place 60h after stirring; Inspection viscosity changes measuring result such as table 2.Viscosity changes less than 3% be excellent, less than 8% be very, is to be poor greater than 30% less than 15%.
The stability in storage of resin is measured: embodiment 1-14 and the prepared reaction resin of Comparative Examples 1-2 are placed on respectively in 50 ℃ the baking oven and check viscosity change, measuring result such as table 2.The viscosity variation is excellent less than 5%, is good less than 15%, is poor greater than 30%;
The buck stability measurement of resin: the NaOH aqueous solution (mass concentration 5%) that adds mass ratio 5% in the reaction resin that embodiment 1-14 and Comparative Examples 1-2 is prepared; In 60 ℃ baking oven, place 60h after stirring; Inspection viscosity changes measuring result such as table 2.Viscosity changes less than 3% be excellent, less than 8% be very, is to be poor greater than 30% less than 15%.
The sticking power of resin is measured: get the synthetic reaction resin 100g of embodiment and Comparative Examples institute, add 20g Bing Xisuandingzhi and 2g light trigger 1173 and stir, obtain mixture; Mixture is applied on the ABS plastic plate of white, perhaps on the stainless steel plate, covers the PET film more in the above; Coat-thickness 0.02mm, with the high voltage mercury lamp radiation 50s of 1000w, lamp is apart from 30cm; Obtain cured coating, estimate sticking power, measuring result such as table 2 with cross-hatching.Optimum is 0 grade, and the poorest is 5 grades.
Table 2 evaluation result table
Can know by data in the table 2; All obviously be superior to the prepared PUA type reaction resin of Comparative Examples 1-2 by aspects such as the viscosity of the prepared PUA type reaction resin of embodiment of the invention 1-14, water-absorbent, water-fast and acidproof, alkali resistance, stability and sticking power; Those skilled in the art are according to explanation of the present invention; Have the ability through reasonably selecting and make up the raw materials such as (methyl) propenoate of diolefine oligopolymer, polyvalent alcohol, vulcabond and hydroxyl for use, select reasonably reinforced and stepwise reaction order and control the level of response in per stage, can design, soft, the hard hop count order and the molecular conformation of synthetic PUA resin; The performance of adjustment resin; For example the viscosity of resin, molecular weight, to the sticking power of metal or plastics, and the mechanical property of resin etc. makes it to satisfy the certain applications requirement.
The above is merely the preferred embodiments of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all be included within protection scope of the present invention.
Claims (11)
1. PUA type reaction resin; It is characterized in that; Said PUA type reaction resin is terminal hydroxy group diolefine oligopolymer, diisocyanate cpd, optional polyvalent alcohol and contain-and (methyl) propenoate of OH is prepared from; The said reaction resin that makes comprises soft section of diolefine oligopolymer, hard section of double carbamate, and the molecule chain end that contains (methyl) acryloyl-oxy group.
2. PUA type reaction resin according to claim 1 is characterized in that, number sum >=8 of C, S, O atom o'clock in the saturated carbon chains of said polyvalent alcohol, and soft section of prepared said reaction resin also comprises by said saturated carbon chains formed soft section.
3. PUA type reaction resin according to claim 1 and 2 is characterized in that, on average contains 1-5 soft section, 2-6 hard section and 2-4 (methyl) acryloyl-oxy group molecule chain end on the molecular chain of said PUA type reaction resin.
4. PUA type reaction resin according to claim 3 is characterized in that, the mol ratio of said polyvalent alcohol and said terminal hydroxy group diolefine oligopolymer is 0～2: 1; In the said diisocyanate cpd-NCO functional group and said polyvalent alcohol and said terminal hydroxy group diolefine oligopolymer in-mol ratio of OH functional group sum is 6/5～2/1.
5. according to claim 1 or 3 described PUA type reaction resins, it is characterized in that the number-average molecular weight of said terminal hydroxy group diolefine oligopolymer is 800g/mol～6000g/mol, perhaps OH value is 0.3mmol/g～2.5mmol/g.
6. PUA type reaction resin according to claim 5; It is characterized in that; Said terminal hydroxy group diolefine oligopolymer comprises the terminal hydroxy group diolefine oligopolymer that contains the itrile group group, and the weight content of itrile group group is M in the said terminal hydroxy group diolefine oligopolymer that contains the itrile group group, 0＜M≤22%.
7. PUA type reaction resin according to claim 5; It is characterized in that; Said terminal hydroxy group diolefine oligopolymer comprises the terminal hydroxy group diolefine oligopolymer that contains the phenyl ring group, and the weight content of phenyl ring group is X in the said terminal hydroxy group diolefine oligopolymer that contains the phenyl ring group, 0＜X≤18%.
8. PUA type reaction resin according to claim 3 is characterized in that, said polyvalent alcohol is divalent alcohol and/or the trivalent alcohol that contains 2～20 carbon atoms, and the mol ratio of said polyvalent alcohol and said terminal hydroxy group diolefine oligopolymer is 1: 10～2: 1.
9. PUA type reaction resin according to claim 7 is characterized in that said polyvalent alcohol is divalent alcohol and trivalent alcohol, and the ratio of the molar weight of said trivalent alcohol and said divalent alcohol and said terminal hydroxy group diolefine oligopolymer molar weight sum is R, 0＜R≤2.
10. the preparation method of a PUA type reaction resin as claimed in claim 1 is characterized in that, may further comprise the steps:
Generate end group with terminal hydroxy group diolefine oligopolymer, optional polyvalent alcohol and diisocyanate cpd reaction and be-preform of NCO;
With containing-(methyl) propenoate of OH and the said PUA type reaction resin of preform reaction generation.
11. preparation method according to claim 9 is characterized in that,
Preparing said end group comprises for the step of the preform of-NCO:
Said terminal hydroxy group diolefine oligopolymer behind the decompression dehydration is mixed with optional polyvalent alcohol and optional catalyzer heated and stirred, form solution A; In solution A, add diisocyanate cpd, elevated temperature is not to being higher than 70 ℃ gradually, and reaction 1～2.5h obtains the preform of end group for-NCO; Perhaps
Diisocyanate cpd is mixed with optional polyvalent alcohol; Be not higher than 70 ℃ of following stirring reaction 0.5～2h in temperature; Form solution B, said terminal hydroxy group diolefine oligopolymer and optional catalyzer behind the adding decompression dehydration, controlled temperature is to not being higher than 70 ℃; Stirring reaction 1～2.5h obtains the preform of end group for-NCO;
With contain-(methyl) propenoate of OH comprises with the said PUA type reaction resin of preform reaction generation:
In the preform of said end group, add and contain-(methyl) propenoate of OH and optional thinner,, promptly get said PUA type reaction resin at 50～70 ℃ of stirring reaction 1～3h for-NCO.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892890A (en) * | 2014-09-30 | 2015-09-09 | 深圳市浩力新材料技术有限公司 | Ultra-flexible polyurethane acrylate resin and liquid-state optical adhesive composition thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892890A (en) * | 2014-09-30 | 2015-09-09 | 深圳市浩力新材料技术有限公司 | Ultra-flexible polyurethane acrylate resin and liquid-state optical adhesive composition thereof |
| CN106674476A (en) * | 2017-01-22 | 2017-05-17 | 江苏旭泽技术有限公司 | Low-shrinkage UV curing PUA resin, as well as preparation method and application thereof to preparation of hot bending membrane |
| CN109206587A (en) * | 2017-06-30 | 2019-01-15 | 第工业制药株式会社 | Polymer resin composition and its solidfied material |
| CN112048051A (en) * | 2019-06-05 | 2020-12-08 | 万华化学（北京）有限公司 | Polyurethane acrylate resin and preparation method thereof |
| CN113278125A (en) * | 2021-05-28 | 2021-08-20 | 南京玖泰新材料科技有限公司 | Photo-curing polyurethane and application thereof |
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