CN1028867C - Processes for preparing high-hard resin and polymerizable monomer - Google Patents
Processes for preparing high-hard resin and polymerizable monomer Download PDFInfo
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- CN1028867C CN1028867C CN 90101780 CN90101780A CN1028867C CN 1028867 C CN1028867 C CN 1028867C CN 90101780 CN90101780 CN 90101780 CN 90101780 A CN90101780 A CN 90101780A CN 1028867 C CN1028867 C CN 1028867C
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Abstract
The high surface hardness transparent resin comprises a crosslinked polymer prepared by copolymerizing a monomer A (represented by the formula I) and a monomer (B). In formular I, R is an aliphatic residue having or not having an oxygen atom, an alicyclic ring, a heterocyclic ring or an aromatic ring, or an alicyclic residue, l is 0 or 1, each of i and j is an integer of 1 or more, and when l=0, i=j=1, when l=1, (i+j) is 4 or less, when j=1, X is oxygen or sulfur, when j>/=2, all X's are oxygen or sulfur, or one X is oxygen and the other X's are sulfur, or one X is sulfur and the other X's are oxygen. The monomer (B) contains one or more functional groups of at least one kind selected from the group consisting of a,b,c.
Description
The invention relates to the method for preparing transparent resin, this resin has high surface hardness and good anti-scratch, heat-resisting and chemical resistant properties is arranged; The invention still further relates to a kind of shield cap, optical lens and the hard coating material of going up luminescent material, imagescope that contains above-mentioned resin; And relating to method for preparing this resin and the method for preparing novel polymerisable monomer, this monomer is as the raw material of highly hard transparent resins.
Methacrylic resin, polycarbonate resin, and polystyrene resin, in the transparency, shock resistance, workability and mass production aspect all are fabulous materials, thereby, so far they have been used as vehicle, house, the window glass in school and gymnasium etc., the washboard in corridor, the last luminescent material of balcony, display equipment (for example various panel boards, computer and lcd tv display and vending machine front baffle plate etc.) shield cap, optical lens, the cover of luminaire, label, safety glasses, light is word CD pedestal etc. not, particularly work as above-mentioned resin and be used as luminescent material, when display equipment shield cap and optical lens, from visibility and angle attractive in appearance, this resin has the good transparency except needs, optical physics, physical strength, outside the toughness etc., also need to have the scuff resistance (being high surface hardness) of height, chemical resistant properties, thermotolerance etc.
But above-mentioned common transparent resin all is a simple linear polymer, therefore their surface hardness, chemical resistant properties, thermotolerance are not enough, in addition, even these resins are coated with surface hardness and the chemical resistant properties of improving them with hard coating material, always do not reach the degree of enough satisfaction yet.
In order to address these problems, a kind of transparent resin has been proposed now, it is a kind of polymkeric substance with crosslinking structure, for example Diethylene Glycol diallyl carbonate resin or urethane polyacrylic ester (Japanese Patent is open, and publication number is 3610/1986 and 75022/1988).
But, these resins that proposed are by allyl group, acrylic, or methacrylic acid group carries out polymerization mutually and makes, and thereby there are more following problems in their rate of polymerization all on identical level, be that polyreaction is difficult to control, the tendency out of control that responds, and in order to obtain the polymkeric substance that condition of surface is good and polymerization should tail off, polymerization cycle needs long.
Purpose of the present invention provides a kind of high rigidity that is used to prepare, the method for transparent resin, and this resin possesses following performance: high surface hardness, good chemical resistance and thermotolerance, the easy control of polyreaction etc.
Another object of the present invention provides a kind of preparation monomer methods, and this monomer has polymerisable group, and its polymerization rate is lower than acrylic, methacrylic acid group and ethenylphenyl and copolymerization this monomer and these groups are fine.Such monomer can polymerization obtain a kind of high surface hardness that has, all good polymkeric substance of the transparency and thermotolerance and/or chemical resistant properties.
The present inventor has carried out sufficient research for addressing the above problem.
Result of study has been found that uppity reaction can be controlled at an easy rate during polyreaction, and polymerization reaction time can obviously shorten; And this transparent resin (have high surface hardness, contain crosslinked polymkeric substance of the presently claimed invention) can obtain with the method that another kind of polymerizable groups with high rate of polymerization combines by this polymerizable groups of pseudoallyl phenyl that low polymerization rate is arranged; just with compound that 2 or a plurality of different propylene phenyl are arranged in the molecule with have another compound of one or more acryls, methacryloyl, vinyl phenyl to carry out copolymerization, its radical polymerization performance of the latter's group will be higher than the pseudoallyl phenyl.
In addition, have found that it is scuff resistance, heat-resisting and chemical resistant properties that resin of the present invention has high surface hardness.Therefore, the sheet material of this resin can be used for the shield cap of last luminescent material, display equipment (indicating meter of for example various panel boards, computer and LCD TV, and vending machine front apron etc.) of washboard, the balcony in window glass, the corridor in vehicle, house, school and gymnasium and the optical lens of being done by the lensing forming polymer.Find also that in addition resin of the present invention also can be used as the coating film film, be hard coating material.This resin is applied on resin, metal or the wood material, and resulting hard coat has excellent anti-scratch and chemical resistant properties after polymerization.
And the present invention has also had been found that the monomer that a kind of like this novelty is arranged, and it can prepare highly hard transparent resins, and this monomer has pseudoallyl dimethyl benzyl and pseudoallyl phenoxy group.The present invention has also found this novelty monomer methods of preparation.
According to the present invention, that preparation contains is crosslinked, the method for high rigidity, transparent resin is the copolymerization that comprises monomer (A) and monomer (B), and monomer (A) is represented with following formula I:
Wherein, R is a kind of aliphatic group or a kind of alicyclic group that is with or without Sauerstoffatom, alicyclic ring, heterocycle or an aromatic nucleus, and 1 is 0 or 1, i and j respectively do for oneself 1 or greater than 1 integer, when 1=0, i=j=1, (i+j) is 4 or less than 4 when l=1, when j=1, X is oxygen or sulphur, and when j 〉=2, all X are oxygen or sulphur, perhaps X is an oxygen and other all X is a sulphur, and perhaps X is a sulphur and other all X is an oxygen:
Monomer (B) has one or more functional groups, wherein has at least a class to be selected from the group of being made up of following groups, that is:
CH
2=CH-C(O)-and O-, CH
2=C(CH
3)-C(O)-O-, and
CH
2＝CH
This cross-linked polymer can contain following (II), (III), (IV) and 1 or the structural unit of (V):
Wherein, R
1Be that hydrogen or methyl, R are the aliphatic groups that is with or without Sauerstoffatom, alicyclic ring, heterocycle or an aromatic nucleus, perhaps alicyclic group, l is 0 or 1, i and j respectively do for oneself 1 or greater than 1 integer, when l=0, i=j=1, (i+j) is 4 or less than 4 when l=1, when j=1, X is oxygen or sulphur, and when j 〉=2, all X are oxygen or sulphur, perhaps 1 X is an oxygen and another one X or remaining X are sulphur, or X is a sulphur and another one X or remaining X are oxygen.
Copolyreaction can be undertaken by cast polymerized method.For 1 normal pseudoallyl phenyl, CH
2=CH-C(O)-O-, CH
2=C(CH
3)-C-(O)-O-reaches
CH
2=CH
Total amount be 0.5～10 equivalent.
This method can be implemented by the method for free radicals copolymerization reaction.For example, carry out irradiation, if desired, can use radical polymerization initiator by heating or with ultraviolet ray or certain radiation.When with ultraviolet ray, can use photosensitizers.
In the above-mentioned method for preparing resin, monomer (A) can be a kind of for selecting at least the compound of (IV) and (V) from molecular formula:
Wherein, at pseudoallyl-α, the substituting group on the aromatic ring of α-Er Jiajibianji is in a position or contraposition; At the substituting group on the aromatic ring of pseudoallyl phenoxy group then on contraposition, a position or ortho position,
R wherein is H-or CH
3-, at pseudoallyl-α, the substituting group on the aromatic nucleus of α-Er Jiajibianji is in a position or contraposition, and the substituting group on the aromatic nucleus of pseudoallyl phenoxy group is in contraposition, on a position or the ortho position.
Monomer (A) can be by isopropenyl phenol and pseudoallyl-α, α-Er Jiajibianji isocyanate reaction and make carboxylamine generation esterification and a kind of compound of obtaining, this esterification be in isopropenyl phenol phenolic hydroxyl group with at pseudoallyl-α, take place between the isocyanate group in the α-Er Jiajibianji isocyanic ester.
In addition, monomer (A) also can be by the resulting a kind of compound of the ring-opening reaction of epoxy or thiirane.This ring-opening reaction is to carry out between isopropenyl phenol and a kind of compound, this compound that carries out ring-opening reaction has and a kind ofly is with or without a Sauerstoffatom, alicyclic ring, heterocyclic aliphatic group or has a kind of alicyclic group, it has one or two to be to be selected from epoxy or thiirane, carry out the esterification of carbamic esterification or thiocarbamate after the ring-opening reaction again, these esterifications be generated by ring-opening reaction-OH or-SH base and pseudoallyl-α, carry out between the isocyanate group on the α-Er Jiajibianji isocyanic ester.
In addition, monomer (A) can also be by carrying out the resulting a kind of compound of etherification reaction between isopropenyl phenol and a kind of compound, this compound that carries out etherification reaction had both contained one or more halogenated alkyls, contain again one or more-OH and/or-the SH base, this haloalkyl can react with the phenolic hydroxyl group in the isopropenyl phenol, and should-OH and/or-SH is connected a kind of Sauerstoffatom that is with or without, alicyclic ring, the aliphatic group of heterocycle or aromatic nucleus, or be connected on a kind of alicyclic group, make it between halogenated alkyl and phenol alkyl, etherification reaction to take place, and then by-OH and/or-SH and pseudoallyl-α, carry out the esterification of urethane reaction and/or thiocarbamate between the isocyanate group on the α-Er Jiajibianji isocyanic ester.
The molecule formula I
(wherein X is Sauerstoffatom or sulphur atom, R is a kind of aliphatic group or a kind of alicyclic group that is with or without Sauerstoffatom, alicyclic ring, heterocycle or aromatic nucleus, l is 0 or 1, i and j respectively do for oneself 1 or greater than 1 integer, when l=0, i=j=1, the value of (i+j) is 4 or less than 4, when j=1, X is oxygen or sulphur when l=1, when j 〉=2, all X are oxygen or sulphur, or one of them X is oxygen, and another X or other X are sulphur, perhaps an X is a sulphur, the oxygen of another X or other X) monomer (A) can be by molecular formula:
Compound and molecular formula be:
Compound react and prepare, resulting monomer can be the compound of following molecular formula
Wherein, l is 0 or 1, R
3Be-H or-CH
3, at pseudoallyl-α, the substituting group on the aromatic nucleus of α-Er Jiajibianji is in a position or contraposition, and the substituting group on the aromatic nucleus of pseudoallyl phenoxy group is at contraposition, a position or ortho position, i=j=1, and R=-CH
2-
The monomer of molecule formula VI
(l is 0 or 1 in the formula, R is-H or-CH
3At pseudoallyl-α, substituting group on the aromatic nucleus of α-Er Jiajibianji is in a position or contraposition, substituting group on the aromatic nucleus of pseudoallyl phenoxy group is in contraposition, between the position or the ortho position on, this monomer can pass through 3-pseudoallyl-α, α-Er Jiajibianji isocyanic ester or 4-pseudoallyl-α, α-Er Jiajibianji isocyanic ester and following a kind of compound reaction and prepare, this compound is selected from the 4-isopropenyl phenol, the 3-isopropenyl phenol, the 2-isopropenyl phenol, 2-(4-pseudoallyl phenoxy group) ethanol, 2-(3-pseudoallyl phenoxy group) ethanol, 2-(2-pseudoallyl phenoxy group) ethanol, 2-(4-pseudoallyl phenoxy group)-the 1-methyl ethanol, 2-(3-pseudoallyl phenoxy group)-the 1-methyl ethanol, with 2-(2-pseudoallyl phenoxy group)-the 1-methyl ethanol, this reaction is the formation reaction of urethanum.
The ratio of isocyanate group and isopropenyl phenol or hydroxy ethers, preferably 0.8～1.1 equivalence ratio, 1 equivalent.
This reaction can be carried out under the situation that is with or without the solvent existence, and this solvent is an inert to reaction raw materials, and this reaction can be carried out under the situation that catalyzer exists or do not have catalyzer to exist in addition, and this catalyzer can promote the generation of urethanum.
Promote to generate the catalyst levels of urethanum, the weight in isocyanic ester is preferably 0.01～5%.
Temperature of reaction is preferably 30～150 ℃.
The present invention also provides a kind of last luminescent material of above-mentioned highly hard transparent resins, shield cap, optical lens and hard coating material of indicating meter of containing.
Hard coating material of the present invention can be about to the monomer (A) of molecule formula I in order to the preparation of below method
(definition of R wherein, X, l, i and j all as mentioned above) mixes with monomer (B), and monomer (B) contains one or more functional groups, and wherein at least a is to be selected from the group that following groups is formed: CH
2=CH-C(O)-and O-, CH
2=C(CH
3)-C(O)-O-and CH
2=CH
, contain the total amount of this functional group, with respect to 1 normal pseudoallyl phenyl, this total amount is 0.5～10 equivalent.Said mixture is coated on the matrix, and makes it to take place Raolical polymerizable, if desired, also can add radical polymerization initiator and/or photosensitizers by heating, ultraviolet ray or radiation (as gamma-rays).
By following molecule formula I:
(X wherein, R, l, i and j's is described as defined above) exemplary of represented monomer (A) comprising: (1) is a kind of by isopropenyl phenol and pseudoallyl-α, the α-Er Jiajibianji isocyanic ester reacts resulting compound, this reaction is phenolic hydroxyl group and the pseudoallyl-α in isopropenyl phenol, the carbamic esterification of being carried out between the isocyanate group in the α-Er Jiajibianji isocyanic ester, (2) be the resulting compound of a kind of ring-opening reaction by epoxy or thiirane, this ring-opening reaction is to carry out between isopropenyl phenol and a kind of compound, this compound has a kind of Sauerstoffatom that is with or without, alicyclic ring, heterocyclic aliphatic group or a kind of alicyclic group, this base has one or two to select from epoxy or thiirane, carry out the esterification of carbamic esterification or thiocarbamate after the ring-opening reaction again, these esterifications be generated by ring-opening reaction-OH or-SH base and pseudoallyl-α, carry out between the isocyanate group on the α-Er Jiajibianji isocyanic ester.(3) be a kind of by carrying out the resulting compound of etherification reaction between isopropenyl phenol and the following so a kind of compound, this compound that carries out etherification reaction had both contained one or more haloalkyls, contain again one or more-OH and/or-the SH group, this halogenated alkyl can react with the phenolic hydroxyl group in the isopropenyl phenol, and should-OH and/or-SH is connected to be with or without a Sauerstoffatom, alicyclic ring, a kind of aliphatic group of heterocycle or aromatic nucleus, perhaps on a kind of alicyclic group, thereby make it between halogenated alkyl and phenolic hydroxyl group, etherification reaction to take place, and then by-OH and/or-SH and pseudoallyl-α, carry out the urethane reaction between the isocyanate group on the α-Er Jiajibianji isocyanic ester and/or vulcanize carbamic esterification.
In general, the molecular weight of the R in the molecule formula I is low more good more, and this is related to the three-dimensional stability of structure, and the molecular weight of R is preferably between 25～500.
Contain an aliphatic group or alicyclic group and (and one or two epoxy group(ing) and thiiranes group are arranged, and contain or do not contain a Sauerstoffatom, alicyclic ring, heterocycle, the example of compound or aromatic nucleus) comprises: oxyethane, propylene oxide, 2, the 3-butylene oxide ring, 3, the 4-butylene oxide ring, 2,3-epoxy pentane, 1,2-epoxy hexane, epoxy cyclohexane, the oxirane ring heptane, the oxirane ring octane, Styrene oxide 98min., 2-phenyl-1, the 2-propylene oxide, the tetramethyl-ring oxidative ethane, Epicholorohydrin, epibromohydrin, Racemic glycidol, 1,2-epoxy-3-phenoxypropane, the Racemic glycidol isopropyl ether, cured ethylene, propylene sulfide, sulfide isobutene, sulfuration 2, the 3-butylene, sulfuration vinylbenzene, ethylene glycol diglycidylether, butanediol diglycidyl ether, neopentylglycol diglycidyl ether, spiral shell glycol diglycidylether, the trihydroxymethyl propane triglycidyl ether, bisphenol A epoxide resin, tetrabromo bisphenol-a epoxy resin, bisphenol F epoxy resin, bisphenol-s epoxy resin, the alicyclic diepoxy acetal, the alicyclic diepoxy adipic acid ester, the alicyclic diepoxy carboxylicesters, the vinyl cyclohexane dioxide, o-phthalic acid diglycidyl ester, the tetrahydrophthalic acid 2-glycidyl ester, the hexahydrophthalic acid 2-glycidyl ester, right-glycidyl oxybenzene formic acid glycidyl ester (glycidyl P-glycidyloxybenzoate), the propanedioic acid 2-glycidyl ester, the succsinic acid 2-glycidyl ester, the pentanedioic acid 2-glycidyl ester, the hexanodioic acid 2-glycidyl ester, N, the N-diglycidylaniline, and diglycidyl glycolylurea.
Contain a kind of aliphatic group or a kind of alicyclic group, contain one or more halogenated alkyls that can react and one or more-OH with the phenol alkyl in the different propylene phenol and/or-SH, and contain or do not contain a Sauerstoffatom, alicyclic ring, heterocycle, or the example of the compound of aromatic nucleus comprises: ethylene iodohydrin, bromo ethanol, the bromo propyl alcohol, 3-bromo-1, the 2-propylene glycol, the bromo hexanol, chloro ethanol, the chloro propyl alcohol, 3-chloro-1, the 2-propylene glycol, chlorobutanol, the chloro hexanol, 1,4-two bromos-2, the 3-butyleneglycol, 2,3-two bromos-1, the 4-butyleneglycol, 1,4-two bromos-2-butanols, 1,3-two bromos-2-propyl alcohol, 2, the 3-di bromo propanol, 1,3-dichloro--2-propyl alcohol, two bromo neopentyl glycol, the chloro propylmercaptan, 3-chloro-2-hydroxyl propylmercaptan and 3-bromo-2-hydroxyl propylmercaptan.
Monomer (A) can obtain by the ring-opening reaction of known urethane reaction, Thiourethane reaction, etherification reaction and epoxy group(ing) or thiirane by using above-claimed cpd (1), (2) and (3).When using solvent, then after building-up reactions, should distill to remove and desolvate.If desired, also will carry out purifying, resulting thus monomer (A) is equipped with the Raolical polymerizable of doing subsequently and uses.
The exemplary of monomer (A) comprises with following molecular formula (VI) and represented compounds such as (VII):
(wherein, the substituting group on the aromatic nucleus of pseudoallyl dimethyl benzyl is position or contraposition betwixt, and the substituting group on the aromatic nucleus of pseudoallyl phenoxy group is to be positioned at its ortho position, a position or contraposition)
(wherein, R
2Be-H or-CH
3, at pseudoallyl-α, the substituting group on the aromatic nucleus of α-Er Jiajibianji is position or contraposition betwixt, the substituting group on the aromatic nucleus of different propylene phenoxy group be at its ortho position, a position or contraposition).
The other example of monomer (A) is by as shown in the formula expression:
(wherein, R
4Be-H or-CH
3, at pseudoallyl-α, the substituting group on the aromatic nucleus of α-Er Jiajibianji is position or contraposition between it, and the substituting group on the aromatic nucleus of pseudoallyl phenoxy group is contraposition, a position or the ortho position at it),
(wherein, at pseudoallyl-α, the substituting group on the aromatic nucleus of α-Er Jiajibianji is in a position or contraposition, and the substituting group on the aromatic nucleus of pseudoallyl phenoxy group is at contraposition, a position or ortho position),
On the aromatic nucleus in above-mentioned two molecular formula, substituent position is defined the same with the front.
In the present invention, (this functional group is from CH in molecule one or more functional groups to be arranged
2=CH-C(O)-and O-, CH
2=C(CH
3)-C(O)-O-, and CH
2=CH
In select at least a kind of) monomer (B), be the ester of a kind of acrylic acid ester or methacrylic acid, or a kind of cinnamic derivative.The example of monomers B comprises: methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, propyl acrylate, propyl methacrylate, the vinylformic acid isopropyl esters, the methacrylic acid isopropyl esters, the vinylformic acid cyclohexyl ester, the methacrylic acid cyclohexyl ester, benzyl acrylate, benzyl methacrylate, vinylformic acid methoxy ethyl ester, methacrylic acid methoxy base ethyl ester, vinylformic acid ethoxyethyl group ester, the methacrylic acid oxyethyl group, ethyl ester, vinylformic acid 2-hydroxyethyl ester, methacrylic acid 2-hydroxyethyl ester, vinylformic acid 2-hydroxy-propyl ester, methacrylic acid 2-hydroxy-propyl ester, 1, the 4-single-butanediol acrylate, 1,4-butyleneglycol monomethacrylates, glycidyl acrylate, glycidyl methacrylate, vinylbenzene, vinyl toluene, chlorostyrene, bromostyrene, the chloro vinyl toluene, methoxy styrene, ethylene glycol diacrylate, Ethylene glycol dimethacrylate, the diacrylate binaryglycol ester, diethyleneglycol dimethacrylate(DEGDMA), the diacrylate propylene glycol ester, the dimethyl allene acid propylene glycol ester, dipropylene glycol diacrylate, dipropyleneglycol dimethacrylate, 2, two (the 4-acryloyl-oxy ethoxyl phenenyl) propane of 2-, 2, two (the 4-methacryloxypropyl ethoxyl phenenyl) propane of 2-, 2, two (the 4-acryloyl-oxy diethoxy phenyl) propane of 2-, 2, two (the 4-methacryloxypropyl diethoxy phenyl) propane of 2-, 2, two (the 4-acryloyl-oxy propyl group oxygen phenyl) propane of 2-, 2, two (the 4-methacryloxypropyl oxygen phenyl) propane of 2-, diacrylate 1, the 3-butanediol ester, dimethacrylate 1, the 3-butanediol ester, diacrylate 1, the 3-butanediol ester, dimethacrylate 1, the 4-butanediol ester, diacrylate 1,6-hexylene glycol ester, dimethacrylate 1,6-hexylene glycol ester, diacrylic acid pentyl diol ester, the dimethacrylate DOPCP, neopentyl glycol hydroxy new pentane acid ester diacrylate, the spiral shell omega-diol diacrylate, spiral shell glycol dimethacrylate, epoxy acrylate, epoxy methacrylates, 2-vinylformic acid [2-[1,1-dimethyl-2-[(1-oxo-2-propenyl) oxygen] ethyl] 5-ethyl-1,3-diox-5-yl] methyl ester, Viscoat 295, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, two (acrylyl oxy-ethyl) hydroxyethyl isocyanurate ester, two (methylacryoyloxyethyl) hydroxyethyl isocyanurate ester, three (acrylyl oxy-ethyl) chlorinated isocyanurates, three (methylacryoyloxyethyl) chlorinated isocyanurates, tetramethylol methane tetraacrylate, tetramethylolmethane tetramethyl-acrylate, tetramethylolmethane six acrylate, Dipentaerythritol hexamethyl acrylate, methyl three (vinylformic acid oxygen oxyethyl group) silane, the glycerine diacrylate, the glycerine dimethacrylate, glycerine methacrylic ester acrylate, the dibromoneopentyl glycol diacrylate, the dibromoneopentyl glycol dimethacrylate, Vinylstyrene, the urethanum acrylate, the urethanum methacrylic ester, 1,1,3,3,5,5-six (acryloyl-oxy) encircles triguaiacyl phosphate, 1,1,3,3,5,5-six (methacryloxypropyl) encircles triguaiacyl phosphate, 1,1,3,3,5,5-six (acryloyl ethylene dioxy) encircles triguaiacyl phosphate, and 1,1,3,3,5,5-six (methacryloyl ethylene dioxy ring triguaiacyl phosphate.
The transparent resin of high surface hardness of the present invention can carry out copolyreaction with another kind of monomer (B) with the monomer (A) of formula I and prepare.Monomer (A) is:
(wherein, X is Sauerstoffatom or sulphur atom, R be contain or do not contain a kind of aliphatic group of Sauerstoffatom, alicyclic ring, heterocycle or an aromatic ring or a kind of alicyclic group, l is 0 or 1, i and j respectively do for oneself 1 or greater than 1 integer, when l=0, i=j=1, when l=1, the value of i+j be 4 or less than 4).Monomers B has one or more functional groups, and this functional group is from CH
2=CH-C(O)-and O-, CH
2=C(CH
3)-C(O)-O-reaches, CH
2=CH
At least select a kind of in the group of being formed.
In order to regulate the purpose of viscosity etc., except above-mentioned monomer (A), can also use monomer with pseudoallyl phenyl, this monomeric example is di isopropenylbenzene, N-(3-pseudoallyl-α, α-Er Jiajibianji)-and 2-acryloyl-oxy carbamate and N-(3-pseudoallyl-α, α-Er Jiajibianji)-2-methacryloxypropyl carbamate.
In this copolyreaction, in the above-mentioned monomer mixture, its pseudoallyl and CH
2=CH-C(O)-and O-, CH
2=C(CH
3)-C(O)-O-, or CH
2=CH
Ratio to depend on the type of functional group in this monomer and this monomeric structure, pseudoallyl phenyl and CH
2=CH-C(O)-and O-, CH
2=C(CH
3)-C(O)-O-, and CH
2=CH
The ratio of total amount, be that 0.5～10 normal ratio is carried out copolyreaction preferably with 1 equivalent.
Copolyreaction of the present invention is a kind of radical copolymerization, and it can or use ultraviolet ray or gamma-rays or method that both are used in combination are finished with the method for thermopolymerization.
Under the situation of thermopolymerization, can with or need not a kind of known radical polymerization initiator, the example of this initiator comprises superoxide, for example benzoyl peroxide, chloro benzoyl peroxide, peroxidation dimethyl isopropyl ester, peroxidation carbonic acid two-2-(ethyl hexyl) ester and peroxidation PIVALIC ACID CRUDE (25) tertiary butyl ester, also comprise a kind of azo-compound, Diisopropyl azodicarboxylate for example, the consumption of initiator is 0.01 to 5%(weight).
Using under the ultraviolet situation; can with or need not a kind of known photosensitizers, the example of this photosensitizers comprises benzoylation compound, benzoin methyl ether, bitter almond oil camphor ethyl ether, bitter almond oil camphor propyl ether, bitter almond oil camphor isobutyl ether, 2-hydroxyl-2-benzoyl propane, Diisopropyl azodicarboxylate, dibenzoyl, thioxanthone and diphenyl disulfide thing.The consumption of photosensitizers is a 0.01-5%(weight).
Use under the situation of radiation such as gamma-rays etc., in general, always do not need polymerization starter etc.
In the present invention, the sheet material of highly hard transparent resins or lens can prepare with arbitrary known method.A kind of typical method is a cast poymerization, for example, above-mentioned monomeric mixture is mixed with enough radical polymerization initiator or photosensitizers, carries out froth breaking thereupon.Then, this mixture is poured in glass or the metal die, this mould matches with packing ring or pad.Solidify with heating or ultraviolet ray or irradiation with radiation then.Much less, before the polymerization, can add some additives, the example of additive comprises: the consumption of uv-absorbing agent, oxidation retarder, dyestuff, near infrared absorbent, releasing agent and static inhibitor, these additives should be advisable not hinder polyreaction and solidified scope.
When preparing film with highly hard transparent resins, can use the known method for preparing film, just, radical polymerization initiator or photosensitizers are added in the above-mentioned monomer mixture, if desired, useable solvents is diluted this mixture.Then, this mixture is coated on a certain matrix, matrix can be made by resin, metal, timber or other materials similar, and coating method can be used roller coating, spraying, flow coat, dip-coating or other similar method.When using solvent, solvent evaporation is heating and curing then, or with ultraviolet ray or radiation curing.In the case, before the polymerization, can add some additive, filler etc. in mixture, the example of additive comprises: uv-absorbing agent, oxidation retarder, dyestuff, pigment, near infrared absorbent, static inhibitor and mineral compound fine particle.The consumption of these additives should be grasped in not hindering polyreaction and solidified scope.
The sheet material of resulting highly hard transparent resins can be used as the shield cap of lustering agent, indicating meter etc. thus, and they have high anti-scratch, chemical resistant properties, thermotolerance and good processibility.In addition, when the mould that is used for making lens carries out polyreaction, or, resin adds man-hour when cutting or polish; Can obtain having the optical lens of the identical characteristics in the above-mentioned situation.
In addition, this highly hard transparent resins can be used as coated material, promptly is used in the hard coating material on other resin, metal, timber or other analogous material, and this hard coating material has excellent anti-scratch, chemical resistant properties etc.
The polymerisable monomer of novelty of the present invention is above-mentioned monomer (A), the monomeric exemplary of this novelty comprises: [N-(3-pseudoallyl-α, α-Er Jiajibianji)] (4-pseudoallyl phenyl) carbamate, N-(3-pseudoallyl-α, α-Er Jiajibianji)] (3-isopropyl phenyl) carbamate, [N-(3-pseudoallyl-α, α-Er Jiajibianji)] (2-pseudoallyl phenyl) carbamate, [N-(4-pseudoallyl-α, α-Er Jiajibianji)] (4-pseudoallyl phenyl) carbamate, [N-(4-pseudoallyl-α, α-Er Jiajibianji)] (3-pseudoallyl phenyl) carbamate, [N-(4-pseudoallyl-α, α-Er Jiajibianji)], (2-pseudoallyl phenyl) carbamate, N-(3-pseudoallyl-α, α-Er Jiajibianji) [2-(4-pseudoallyl phenyl) ethyl] carbamate, N-(3-pseudoallyl-α, α-Er Jiajibianji) [2-(3-pseudoallyl phenoxy group) ethyl] carbamate, N-(3-pseudoallyl-α, α-Er Jiajibianji) [2-(2-pseudoallyl phenoxy group) ethyl] carbamate, N-(4-pseudoallyl-α, α-Er Jiajibianji) [2-(4-pseudoallyl phenoxy group) ethyl] carbamate, N-(4-pseudoallyl-α, α-Er Jiajibianji) [2-(3-pseudoallyl phenoxy group) ethyl] carbamate, N-(4-pseudoallyl-α, α-Er Jiajibianji) [2-(2-pseudoallyl phenoxy group) ethyl] carbamate, N-(3-pseudoallyl-α, α-Er Jiajibianji) [1-(4-pseudoallyl phenoxy group)-the 1-methylethyl] carbamate, N-(3-pseudoallyl-α, α-Er Jiajibianji)-[1-(3-pseudoallyl phenoxy group)-the 2-methylethyl] carbamate, N-(3-pseudoallyl-α, α-Er Jiajibianji) [2-(2-pseudoallyl phenoxy group)-the 1-methylethyl] carbamate, N-(4-pseudoallyl-α, α-Er Jiajibianji) [1-(4-pseudoallyl phenoxy group)-the 1-methylethyl] carbamate, N-[4-pseudoallyl-α, α-Er Jiajibianji) [2-(3-pseudoallyl phenoxy group)-the 1-methylethyl] carbamate and N-(4-pseudoallyl-α, α-Er Jiajibianji) [1-(2-pseudoallyl phenoxy group)-the 1-methylethyl] carbamate.
Above-mentioned polymerisable monomer of the present invention can be made by following method: with 3-pseudoallyl-α, α-Er Jiajibianji isocyanic ester or 4-pseudoallyl-α, α-Er Jiajibianji isocyanic ester and 2-(4-pseudoallyl phenoxy group) ethanol, 2-(3-pseudoallyl phenoxy group) ethanol, 2-(2-pseudoallyl phenoxy group) ethanol, 2-(4-pseudoallyl phenoxy group)-the 1-methyl ethanol, 2-(3-pseudoallyl phenoxy group)-1-methyl ethanol or 2-(2-pseudoallyl phenoxy group)-(these components are by the 4-isopropenyl phenol to the 1-methyl ethanol, the 3-isopropenyl phenol, or 2-isopropenyl phenol and oxyethane, ethylene bromohyrin or propylene oxide react and obtain), (solvent is: the solvent that reacts with starting material not not existing or exist under the solvent, as hexane, chloroform, benzene or toluene) react, its material rate is 1 normal 4-isopropenyl phenol, the 3-isopropenyl phenol, 2-propenyl phenol or above-mentioned hydroxy ethers are than 0.8-1.0 equivalent, the best normal isocyanic ester of 0.95-1.0, the reaction soln temperature is 30-150 ℃, be preferably 50-100 ℃, there is or do not exist catalyzer (this catalyzer is used for promoting the generation of urethanum), dibutyltin dilaurate for example, catalyst levels is that benchmark measures with the consumption of isocyanic ester, be 0.01-5% weight, be preferably 0.1-3% weight.After reaction is finished, with resulting reaction soln by column type chromatography separating method purifying in addition, thereby can obtain desirable polymerisable monomer of the present invention.
Resin of the present invention has high surface hardness, and the excellent transparency, chemical resistant properties and thermotolerance are arranged.In addition, in processibility, for example the performance that high surface hardness is cut is also fine.
In addition, in the preparation of resin of the present invention, this step of polyreaction is very easy to control, in the molding polymerization, does not take place anyly to peel off, white powder or cracking, and in brief, the mouldability of resin of the present invention is fine, this means to carry out high-precision molding.
Thereby resin of the present invention is applicable to shield cap, optical lens and the hard coating material of making to go up luminescent material, indicating meter.
In addition, when the polymerisable monomer of novelty of the present invention with have the monomer (this group is propenyl, methacrylic acid or ethenylphenyl for example) of the high polymerizable groups of rate of polymerization when carrying out copolymerization, can obtain a kind of transparent resin, this resin has high surface hardness, and has good thermotolerance and workability (for example machining).In addition, in polymerization stage, reaction control is easy to.Thereby monomer of the present invention is the starting material as above-mentioned highly hard transparent resins.
Now, come the present invention is done detailed explanation, but scope of the present invention is in no way limited to these embodiment with reference to following embodiment.
What at first will illustrate a bit is, the umber of each novel polymerisable monomer (A) of the present invention of being mentioned among the embodiment, unless otherwise prescribed outside, its umber is all parts by weight.
Embodiment 1
4-isopropenyl phenol with 13.4 parts, 50 parts toluene, 20.1 3-pseudoallyl dimethylbenzyl based isocyanate of part and 0.3 part dibutyltin dilaurate mix, then this mixture was stirred 3 hours, carry out in order to make reaction, when stirring, the temperature of this reaction soln to be remained on 100 ℃, after reaction is finished, this reaction soln is concentrated, then resulting enriched material is purified through chromatography separating method: thus [N-(3-pseudoallyl-α, α-Er Jiajibianji] (4-pseudoallyl phenyl) carbamate of 20.9 parts white solid obtained.
(empirical formula is C to the ultimate analysis value
22H
25NO
2):
C H N
Measured value (%): 78.59 7.55 4.09
Calculated value (%): 78.77 7.51 4.18
Nucleus magnetic resonance (δ/CDCl
3):
Embodiment 2
Except replace 13.4 parts 4-isopropenyl phenol among the embodiment 1 with 13.4 parts 3-isopropenyl phenol, all repeat embodiment 1 same procedure, thereby prepare [N-(3-pseudoallyl-α, α-Er Jiajibianji] (3-pseudoallyl phenyl) carbamate of 24.1 parts colourless liquid shape.
(empirical formula is C to the ultimate analysis value
22H
25NO
2):
C H N
Measured value (%): 78.68 7.57 4.21
Calculated value (%): 78.77 7.51 4.18
Embodiment 3
Except replace 13.4 parts 4-isopropenyl phenol among the embodiment 1 with 13.4 parts 2-isopropenyl phenol, all repeat the same procedure of embodiment 1, thereby obtain [N-(3-pseudoallyl-α, α-Er Jiajibianji)] (2-pseudoallyl phenyl) carbamate of 22.7 parts of colourless liquid shapes.
(empirical formula is C to the ultimate analysis value
22H
25NO
2):
C H N
Measured value (%): 78.74 7.45 4.15
Calculated value (%): 78.77 7.51 4.18
Embodiment 4
13.4 parts 4-isopropenyl phenols, 50 parts toluene, 20.1 parts 4-pseudoallyl dimethylbenzyl based isocyanate are mixed with 0.3 part dibutyltin dilaurate, then mixture was stirred 3 hours, make the temperature of reaction soln remain on 100 ℃ simultaneously, so that reaction is carried out.Finish after this reaction, this reaction soln is concentrated, then, resulting enriched material is purified through chromatography separating method, thereby obtain [N-(4-pseudoallyl-α, alpha, alpha-dimethyl benzene) benzyl)] (4-pseudoallyl phenyl) carbamate of 23.4 parts white solid.
(empirical formula is C to the ultimate analysis value
22H
25NO
2):
C H N
Measured value (%): 78.62 7.57 4.23
Calculated value (%): 78.77 7.51 4.18
Embodiment 5
Except the 3-isopropenyl phenol with 13.4 parts replaces 13.4 parts the 4-isopropenyl phenol of embodiment 4, all repeat the same procedure of embodiment 4, thereby obtain [N-(4-pseudoallyl-α, α-Er Jiajibianji)] (3-pseudoallyl phenyl) carbamate of 25.2 parts colourless liquid shape.
(empirical formula is C to the ultimate analysis value
22H
25NO
2):
C H N
Measured value (%): 78.52 7.70 4.31
Calculated value (%): 78.77 7.51 4.18
Embodiment 6
Except the 2-isopropenyl phenol with 13.4 parts replaces 13.4 parts the 4-isopropenyl phenol of embodiment 4, all repeat the same procedure of embodiment 4, thereby obtain [N-(4-pseudoallyl-α, α-Er Jiajibianji)] (2-pseudoallyl phenyl) carbamate of 24.9 parts colourless liquid shape.
(empirical formula is C to the ultimate analysis value
22H
25NO
2):
C H N
Measured value (%): 78.67 7.33 4.24
Calculated value (%): 78.77 7.51 4.18
Embodiment 7
2-(4-pseudoallyl phenoxy group with 17.8 parts) ethanol, 30 parts of toluene, 3-pseudoallyl-α of 20.1 parts, the dibutyltin dilaurate of α-Er Jiajibianji isocyanic ester and 0.2 part is mixed, then, this mixture was stirred 1 hour, temperature with reaction soln remains on 80 ℃ simultaneously, so that reaction is carried out.After reaction is finished, this reaction soln is concentrated, then resulting enriched material is purified through chromatography separating method, thereby obtains colourless transparent liquid N-(3-pseudoallyl-α of 35.7 parts, α-Er Jiajibianji) [2-(4-pseudoallyl phenoxy group) ethyl] carbamate.
(empirical formula is C to the ultimate analysis value
24H
29NO
3):
C H N
Measured value (%): 75.73 7.68 3.71
Calculated value (%): 75.96 7.70 3.69
Nucleus magnetic resonance (δ/CDCl
3):
Embodiment 8
Except 2-(3-pseudoallyl phenoxy group with 17.8 parts) ethanol replaces 17.8 parts the 2-(4-pseudoallyl phenoxy group of embodiment 7) the ethanol, all repeat the same procedure of embodiment 7, thereby obtain the N-(3-pseudoallyl-α of 36.3 parts colourless transparent liquid, α-Er Jiajibianji) [2-(3-pseudoallyl phenoxy group) ethyl] carbamate.
(empirical formula is C to the ultimate analysis value
24H
29NO
3):
C H N
Measured value (%): 76.08 7.61 3.66
Calculated value (%): 75.96 7.70 3.69
Nucleus magnetic resonance (δ/CDCl
3):
Embodiment 9
Except 2-(2-pseudoallyl phenoxy group with 17.8 parts) ethanol replaces 17.8 parts the 2-(4-pseudoallyl phenoxy group of embodiment 7) the ethanol, all repeat the same procedure of embodiment 7, thereby obtain N-(3-pseudoallyl-α of 35.5 parts, α-Er Jiajibianji) 2-(2-pseudoallyl phenoxy group) ethyl] the water white transparency shape liquid of carbamate.
(empirical formula is C to the ultimate analysis value
24H
29NO
3):
C H N
Measured value (%): 75.83 7.65 3.63
Calculated value (%): 75.96 7.70 3.69
Nucleus magnetic resonance (δ/CDCl
3):
Embodiment 10
Except 4-pseudoallyl-α with 20.1 parts, the α-Er Jiajibianji isocyanic ester replaces 3-pseudoallyl-α of 20.1 parts of embodiment 7, outside the α-Er Jiajibianji isocyanic ester, all repeat the same procedure of embodiment 7, thereby obtain 34.9 parts N-(4-pseudoallyl)-α, α-Er Jiajibianji)-the water white transparency shape liquid of [2-(4-pseudoallyl phenoxy group) ethyl] carbamate.
(empirical formula is C to the ultimate analysis value
24H
29NO
3):
C H N
Measured value (%): 76.13 7.78 3.76
Calculated value (%): 75.96 7.70 3.69
Nucleus magnetic resonance (δ/CDCl
3):
Embodiment 11
Except 4-pseudoallyl-α with 20.1 parts, the α-Er Jiajibianji isocyanic ester replaces 3-pseudoallyl-α of 20.1 parts of embodiment 8, outside the α-Er Jiajibianji isocyanic ester, all repeat the same procedure of embodiment 8, thereby obtain N-(4-pseudoallyl-α of 35.1 parts, α-Er Jiajibianji) the water white transparency shape liquid of [2-(3-pseudoallyl phenoxy group) ethyl] carbamate.
(empirical formula is C to the ultimate analysis value
24H
29NO
3):
C H N
Measured value (%): 75.99 7.64 3.48
Calculated value (%): 75.96 7.70 3.69
Nucleus magnetic resonance (δ/CDCl
3):
Embodiment 12
Except 4-pseudoallyl-α with 20.1 parts, the α-Er Jiajibianji isocyanic ester replaces 3-pseudoallyl-α of 20.1 parts of embodiment 9, beyond the α-Er Jiajibianji isocyanic ester, all repeat the same procedure of embodiment 9, thereby obtain N-(4-pseudoallyl-α of 35.8 parts, α-Er Jiajibianji) the water white transparency shape liquid of [2-(2-pseudoallyl phenoxy group) ethyl] carbamate.
(empirical formula is pressed C to the ultimate analysis value
24H
29NO
3):
C H N
Measured value (%): 75.84 7.71 3.65
Calculated value (%): 75.96 7.70 3.69
Nucleus magnetic resonance (δ/CDCl
3):
Embodiment 13
Except 2-(4-pseudoallyl phenoxy group with 19.2 parts)-the 1-methyl ethanol replaces 17.8 parts the 2-(4-pseudoallyl phenoxy group of embodiment 7) the ethanol, all repeat the same procedure of embodiment 7, thereby obtain N-(3-pseudoallyl-α of 37.0 parts, α-Er Jiajibianji) the water white transparency shape liquid of [2-(4-pseudoallyl phenoxy group)-1-methylethyl] carbamate.
(empirical formula is C to the ultimate analysis value
25H
31NO
3):
C H N
Measured value (%): 76.15 7.99 3.47
Calculated value (%): 76.30 7.94 3.56
Nucleus magnetic resonance (δ/CDCl
3):
Embodiment 14
Except 2-(3-pseudoallyl phenoxy group with 19.2 parts)-the 1-methyl ethanol replaces 17.8 parts the 2-(3-pseudoallyl phenoxy group of embodiment 8) the ethanol, all repeat the same procedure of embodiment 8, thereby obtain N-(3-pseudoallyl-α of 36.3 parts, α-Er Jiajibianji) [2-(3-pseudoallyl phenoxy group)-the 1-methylethyl) the water white transparency shape liquid of carbamate.
(empirical formula is C to the ultimate analysis value
25H
31NO
3):
C H N
Measured value (%): 76.41 8.08 3.37
Calculated value (%): 76.30 7.94 3.56
Nucleus magnetic resonance (δ/CDCl
3):
Embodiment 15
Except 2-(2-pseudoallyl phenoxy group with 19.2 parts)-the 1-methyl ethanol replaces 17.8 parts of 2-(2-pseudoallyl phenoxy groups of embodiment 9) the ethanol, all repeat the same procedure of embodiment 9, thereby obtain N-(3-pseudoallyl-α of 35.2 parts, α-Er Jiajibianji) the water white transparency shape liquid of [2-(2-pseudoallyl phenoxy group)-1-methylethyl] carbamate.
(empirical formula is C to the ultimate analysis value
25H
31NO
3):
C H N
Measured value (%): 76.18 7.69 3.58
Calculated value (%): 76.30 7.94 3.56
Nucleus magnetic resonance (δ/CDCl
3):
Embodiment 16
Except 4-pseudoallyl-α with 20.1 parts, the α-Er Jiajibianji isocyanic ester replaces 3-pseudoallyl-α of 20.1 parts of embodiment 13, outside the α-Er Jiajibianji isocyanic ester, all repeat the same procedure of embodiment 13, thereby obtain the N-(4-pseudoallyl-α of 35.9 parts water white transparency shape liquid, α-Er Jiajibianji) [2-(4-pseudoallyl phenoxy group)-the 1-methylethyl] carbamate.
(empirical formula is C to the ultimate analysis value
25H
31NO
3):
C H N
Measured value (%): 76.28 8.09 3.75
Calculated value (%): 76.30 7.94 3.56
Nucleus magnetic resonance (δ/CDCl
3):
Embodiment 17
Except 4-pseudoallyl-α with 20.1 parts, the α-Er Jiajibianji isocyanic ester replaces 3-pseudoallyl-α of 20.1 parts of embodiment 14, outside the α-Er Jiajibianji isocyanic ester, all repeat the same procedure of embodiment 14, thereby obtain the N-(4-pseudoallyl-α of 37.1 parts water white transparency shape liquid, α-Er Jiajibianji)-[2-(3-pseudoallyl phenoxy group)-the 1-methylethyl] carbamate.
(empirical formula is C to the ultimate analysis value
25H
31NO
3):
C H N
Measured value (%): 76.49 7.88 3.59
Calculated value (%): 76.30 7.94 3.56
Nucleus magnetic resonance (δ/CDCl
3):
Embodiment 18
Except 4-pseudoallyl-α with 20.1 parts, the α-Er Jiajibianji isocyanic ester replaces 3-pseudoallyl-α of 20.1 parts of embodiment 15, beyond the α-Er Jiajibianji isocyanic ester, all repeat the same procedure of embodiment 15, thereby obtain the N-(4-pseudoallyl-α of 36.4 parts water white transparency shape liquid, α-Er Jiajibianji)-[2-(2-pseudoallyl phenoxy group)-the 1-methylethyl] carbamate.
(empirical formula is C to the ultimate analysis value
25H
31NO
3):
C H N
Measured value (%): 76.32 8.04 3.37
Calculated value (%): 76.30 7.94 3.56
Nucleus magnetic resonance (δ/CDCl
3):
The benzoyl peroxide of 71.2 parts neopentylglycol diacrylates and 0.4 part is added to by the resultant 75.0 parts [N-(3-pseudoallyl-α of the same procedure of embodiment 1, α-Er Jiajibianji] in (4-pseudoallyl phenyl) carbamate, mix fully subsequently, and carry out froth breaking, resulting homogeneous solution is poured in the mould, this mould is made by thick polyvinyl chloride packing ring of 5mm of the folder of the periphery between two 5mm plate glass, clips fixing again with anchor clamps.In the hot-air furnace that polyreaction is used, heat up then, in 1.5 hours, temperature is risen to 150 ℃ from 70 ℃, carry out polyreaction.After the cooling, the transparent resin sheet material that will have smooth surface is deviate from from mould.
Embodiment 20
The benzoyl peroxide of 78.8 parts tetramethylol methane tetraacrylates and 0.5 part is added to 75 parts of same procedure with embodiment 2 obtains [N-(3-pseudoallyl-α, α-Er Jiajibianji)] in (3-pseudoallyl phenyl) carbamate, mix fully and froth breaking thereupon.Then resulting homogeneous solution is poured in the mould, this mould is by the periphery between two 5mm plate glass, sandwich a thick polyvinyl chloride packing ring of 5mm and make, again with anchor clamps with they fix tightlies.In the hot-air furnace that polyreaction is used, in 1.5 hours, temperature is risen to 150 ℃ from 70 ℃ and carry out polyreaction then.After the cooling, the demoulding obtains ganoid transparent resin sheet material.
Embodiment 21
58.7 parts tetramethylol methane tetraacrylates and 0.4 part of benzoyl peroxide are added to 63.3 parts of resulting N-(3-pseudoallyl-α of the same procedure by embodiment 8, α-Er Jiajibianji) in [2-(3-pseudoallyl phenoxy group) ethyl] carbamate, mix fully and froth breaking thereupon, then resulting homogeneous solution is poured in a kind of mould, this mould sandwiches a thick polyvinyl chloride packing ring of 5mm by the periphery between the thick sheet glass of two 5mm and makes, and with anchor clamps they is fixed again.In the hot-air furnace that polyreaction is used, heat up then, in 1.5 hours, temperature is risen to 150 ℃ by 70 ℃ and carry out polyreaction.After the cooling, the demoulding obtains ganoid transparent resin sheet material.
Embodiment 22
The benzoyl peroxide of 43.4 parts Vinylstyrenes and 0.3 part is added to 63.3 parts the N-(3-pseudoallyl-α that obtains by the same procedure of embodiment 8, α-Er Jiajibianji) in [2-(3-pseudoallyl phenoxy group) ethyl] carbamate, carries out thorough mixing and froth breaking thereupon.Then resulting homogeneous solution is poured in the mould, this mould sandwiches a thick polyvinyl chloride packing ring of 5mm by the periphery between two 5mm plate glass and makes, again with anchor clamps with they fix tightlies.The hot-air furnace of using in polyreaction rose to 150 ℃ with temperature from 70 ℃ and carries out polyreaction in 1.5 hours then.After the cooling, the demoulding obtains ganoid transparent resin sheet material.
Embodiment 23
The benzoyl peroxide of 49.5 parts trimethylolpropane trimethacrylates and 0.3 part joined 65.6 parts the resulting N-(3-pseudoallyl-α of the same procedure by embodiment 14, α-Er Jiajibianji) in [2-(3-pseudoallyl phenoxy group)-1-methylethyl] carbamate, mixes fully and froth breaking thereupon.Then resulting homogeneous solution is poured in the mould, this mould sandwiches a thick polyvinyl chloride packing ring of 5mm by the periphery between two 5mm plate glass and makes.Again with anchor clamps with they fix tightlies.In the hot-air furnace of poly-reaction usefulness, heat up then, in 1.5 hours, temperature is risen to 150 ℃ from 70 ℃ and carry out polyreaction.After the cooling, the demoulding obtains ganoid transparent resin sheet material.
Embodiment 24
N-(3-pseudoallyl-α with 13.3 parts, α-Er Jiajibianji)-benzoyl peroxide of 2-methacryloxypropyl carbamate, 77.5 parts tetramethylol methane tetraacrylate and 0.5 part joins 63.3 parts the N-(3-pseudoallyl-α that is made by the same procedure of embodiment 7, α-Er Jiajibianji) in [2-(4-pseudoallyl phenoxy group) ethyl] carbamate, mixes fully and froth breaking thereupon.Then the homogeneous solution that obtains is poured in the mould, this mould sandwiches a thick polyvinyl chloride packing ring of 5mm by the periphery between two 5mm plate glass and makes, again with anchor clamps with they fix tightlies.In the hot-air furnace that polyreaction is used, heat up then, in 1.5 hours, temperature is risen to 150 ℃ from 70 ℃ and carry out polyreaction.After the cooling, the demoulding obtains ganoid transparent resin sheet material.
After prepared transparent resin sheet material had carried out the measurement of various physical propertiess in embodiment 19-24, it the results are shown in the table 1.
Measure various physical propertiess and be to use following method:
(1) outward appearance.The outward appearance of every kind of polymer sheet is with the naked eye done identical observation and is evaluated.Do not have the not coarse polymer sheet in slight crack or surface, represent, and the sheet material with above-mentioned shortcoming is then used " X " expression with " O ".
(2) surface hardness
According to the jis-K-5401 method, the surface hardness of filming with the measurement of pencil test instrument.
(3) thermotolerance
In hot air dryer, temperature is under 120 ℃ with this resin sheet, placed 4 hours, subsequently, and this resin sheet that detects by an unaided eye, its surface sheet material colourless and the nothing distortion then uses " O " to represent, and the sheet material with these defectives is then used " X " expression.
(4) chemical resistant properties
With polymer sheet at room temperature and in Virahol and toluene, soaked 24 hours, subsequently, it is drawn with the HB pencil eraser, with " O " expression, and have the material of some vestige, then use " X " to represent without any the sheet material of vestige.
(5) workability
The sheet material that can grind with spherical grinding machine (be used to process soft-focus lens) is with " O " expression, and the sheet material that can not grind is then used " X " expression.
After table 1 is seen literary composition
Embodiment 25
0.1 part of benzoyl peroxide is joined in the prepared monomer mixture of 30.0 parts the same procedure by embodiment 19, then, this mixture is depressed by having the strainer that the aperture is 5 μ m adding, then this filtrate is poured in the mould of a dioptry for+2 convex lens, this mould is used for Diethylene Glycol diallyl carbonic ether.Subsequently, this mixture is heated up 3 hours sides, rise to 140 ℃ from 70 ℃ and carry out polyreaction, the demoulding obtains the transparent convex lens of smooth surface after the cooling.Pencil hardness test value on this convex lens surface is 4H, and the specific refractory power of being measured by Abb is 1.53.
Embodiment 26
A kind of monomer mixture that 0.2 part benzoyl peroxide and 30.0 parts the same procedure by embodiment 20 is prepared mixes mutually, then this mixture is coated on the steel plate with the coating rod, and making coat-thickness is 50 μ m.Subsequently, this mixture solidified 30 minutes under temperature is 150 ℃.Thereby, on steel plate, obtaining a kind of Clear coating with smooth surface, the pencil hardness test value of this coating film is 8H, and is good by Japanese industrial standards (JISK5400) the checking machine result that tests.In addition, its thermotolerance might as well.(sample placed 10 hours in hot air dryer and under 120 ℃ of temperature and be cited as good heat resistance) without any the sample of problem
Comparative example 1
3.0 parts benzoyl peroxides are added in 100 parts the Diethylene Glycol diallyl carbonic ether, then through mixing and froth breaking, this solution is poured in a kind of mould, this mould sandwiches a thick polyvinyl chloride packing ring of 5mm by the periphery between two 5mm plate glass and makes, and has anchor clamps that they are clipped again.Polyreaction is to carry out in the hot-air furnace that polyreaction is used, and attempts originally that in 3 hours time temperature of reaction is risen to 120 ℃ by 70 ℃ and carries out.Yet in polymerization process, when temperature reached 70 ℃, polyreaction was carried out very fiercely, peel off to cause polymkeric substance and glass mold, and this polymer color flavescence.Have only when the polyreaction heat-up rate and carry out, just can obtain a kind of resin sheet that can not peel off with mould in 10 hours, rising under 120 ℃ the situation from 50 ℃.But, the resin that so obtains, its pencil hardness test value is 3H.
Comparative example 2
Between 18.8 parts-eylylene diisocyanate is added in 20.0 parts the methyl methacrylate, again 0.5 part dibutyl tin laurate is added wherein, 26.0 parts methacrylic acid hydroxyl ethyl ester is joined at leisure, heat simultaneously, so that its internal temperature is 60 ℃, thereby obtain a kind of viscous mixt of methyl methacrylate of urethane compounds, the infrared spectra based on isocyanic ester wherein absorbs almost be can't see.Again 0.3 part benzoyl peroxide is joined in the above-mentioned composition, mix and froth breaking thereupon, and this solution poured in a kind of mould, this mould sandwiches a thick polyvinyl chloride packing ring of 5mm by the periphery between two 5mm plate glass and makes, and they is clipped fixing with anchor clamps again.This polyreaction is to carry out in the hot-air furnace that a kind of polyreaction is used, and attempts originally that in 3 hours time temperature is risen to 120 ℃ by 45 ℃ and carries out.But in polymerization process, when temperature reached 70 ℃, polyreaction was carried out very fiercely, peeled off to cause this polymkeric substance and glass mold.
Comparative example 3
0.5 part benzoyl peroxide is added in 50 parts the Viscoat 295, mix and froth breaking thereupon, then this solution is poured in a kind of mould, this mould is to be made by inserting a thick polyvinyl chloride packing ring of 5mm by the peripheral part between the thick sheet glass of two 5mm, they is clipped fixing with a kind of anchor clamps again.Polyreaction is to carry out in the hot-air furnace that a kind of polyreaction is used, and attempts will be in 3 hours temperature to be risen 140 ℃ from 60 ℃ originally and carries out.But in the initial period of polyreaction, reaction is carried out very fiercely, peels off to cause this polymkeric substance and glass mold.
Table 1
Experimental project EXAMPLE Example embodiment
19 20 21 22 23 24
Outward appearance 000000
9H or 9H or 9H or
Surface hardness 4H 5H 5H
Greater than 9H greater than 9H greater than 9H
Thermotolerance 000000
Chemical resistant properties 000000
Workability 000000
Claims (12)
1, a kind of method for preparing highly hard transparent resins, this resin comprise a kind of crosslinked polymkeric substance that contains, and this method comprises the copolymerization of monomer (A) and monomer (B), and monomer (A) is represented with formula I:
In the formula, R is a kind of aliphatic group or a kind of alicyclic group that is with or without Sauerstoffatom, alicyclic ring, heterocycle or an aromatic nucleus, and 1 is 0 or 1, i and j each naturally 1 or greater than 1 integer, when 1=0, i=j=1; (i+j) is 4 or less than 4, when j=1, X is oxygen or sulphur when l=1; When j 〉=2, all X are oxygen or sulphur, or X is oxygen and another X or all the other X are sulphur, or X is a sulphur and another X or remaining X are oxygen; Monomer (B) has one or more functional groups, and its at least a functional group is selected from by CH
2=CH-C (O)-O-, CH
2=C (CH
3)-C (O)-O-, and CH
2=CH
The group of being formed.
2, according to the process of claim 1 wherein that copolyreaction is to carry out with cast polymerized method.
3, according to the method for claim 2, wherein per 1 normal pseudoallyl phenyl is with respect to CH
2=CH-C(O)-O-, CH
2=C(CH
3)-C(O)-O-, and CH
2=CH-
Total amount be 0.5～10 equivalent.
4, according to the method for claim 3, wherein the reaction that is taken place is a free radical copolymerization.
5, according to the method for claim 4, wherein free radicals copolymerization reaction is with heating, ultraviolet ray or radiation.
6, according to the method for claim 5, wherein use radical polymerization initiator.
7, according to the method for claim 5, wherein when using ultraviolet ray, use photosensitizers.
8, according to each method of claim 1 to 7, wherein monomer (A) is at least a is to select free style IV and (V) represented compound
In the formula, at pseudoallyl-α, the substituting group on the aromatic nucleus of α-Er Jiajibianji is in a position or contraposition, and the substituting group on the aromatic nucleus of pseudoallyl phenoxy group is at a position, contraposition or ortho position.
In the formula, R is-H or-CH
3, at pseudoallyl-α, the substituting group on the aromatic nucleus of α-Er Jiajibianji is in a position or contraposition, and the substituting group on pseudoallyl phenoxy group aromatic nucleus is at contraposition, a position or ortho position.
9, according to the method for claim 8, wherein said monomer (A) is so a kind of compound, it is by a kind of isopropenyl phenol and a kind of pseudoallyl-α, the α-Er Jiajibianji isocyanate reaction, make it in isopropenyl phenol phenolic hydroxyl group with at pseudoallyl-α, carbamic esterification takes place between the isocyanate group in the α-Er Jiajibianji isocyanic ester and a kind of compound of obtaining.
10, method according to claim 8, wherein monomer (A) is by the resulting a kind of compound of the ring-opening reaction of epoxy or thiirane, this ring-opening reaction is to carry out between isopropenyl phenol and a kind of compound, this kind compound that carries out ring-opening reaction has a kind of Sauerstoffatom that contains or do not contain, alicyclic ring, heterocycle or aromatic nucleus, a kind of alicyclic group is perhaps arranged, this base has one or two to be to be selected from epoxy or thiirane, carry out carbamic esterification after the ring-opening reaction again or vulcanize carbamic esterification, these esterifications be generated by ring-opening reaction-OH or-SH base and pseudoallyl-α, carry out between the isocyanate group on the α-Er Jiajibianji isocyanic ester.
11, method according to claim 8, wherein monomer (A) is by carrying out the resulting a kind of compound of etherification reaction between isopropenyl phenol and a kind of compound, this compound that carries out etherification reaction had both contained one or more halogenated alkyls, contain again one or more-OH and/or-SH, this halogenated alkyl can react with the phenolic hydroxyl group in the isopropenyl phenol, and should-OH and/or-SH is connected to be with or without a Sauerstoffatom, alicyclic ring, a kind of aliphatic group of heterocycle or aromatic nucleus, perhaps be connected on a kind of alicyclic group, make it between halogenated alkyl and phenolic hydroxyl group, etherification reaction to take place, and then by-OH and/or-SH and pseudoallyl-α, the isocyanate group on the α-Er Jiajibianji isocyanic ester is carried out the urethane reaction and/or is vulcanized carbamic esterification.
12, according to the process of claim 1 wherein that cross-linked polymer comprises structural unit (II), (III), (IV) and/or (V)
R in the formula
1Be-H or-CH
3, R is a kind of aliphatic group that contains or do not contain Sauerstoffatom, alicyclic ring, heterocycle or an aromatic nucleus, or a kind of alicyclic group, 1 is 0 or 1, and i and j respectively do for oneself 1 or greater than 1 integer, when 1=0, i=j=1, (i+j) is 4 or less than 4, when j=1 when 1=1, X is oxygen or sulphur, and when j 〉=2, all X are oxygen or sulphur, perhaps an X is an oxygen, an X or all the other X are sulphur in addition, and perhaps an X is a sulphur, and another X or all the other X are oxygen.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP48919/89 | 1989-03-01 | ||
| JP4891989 | 1989-03-01 | ||
| JP66240/89 | 1989-03-20 | ||
| JP13155989 | 1989-05-26 | ||
| JP131559/89 | 1989-05-26 |
Related Child Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94116269 Division CN1104631A (en) | 1989-03-01 | 1994-09-22 | A process for preparing a polymerizable monomer for a high-hard transparent resin |
| CN 94116267 Division CN1104650A (en) | 1989-03-01 | 1994-09-22 | A protective cover for display devices comprising a high-hard, transparent resin |
| CN 94116268 Division CN1104651A (en) | 1989-03-01 | 1994-09-22 | A glazing material comprising a high-hard transparent resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1048392A CN1048392A (en) | 1991-01-09 |
| CN1028867C true CN1028867C (en) | 1995-06-14 |
Family
ID=26389267
Family Applications (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90101780 Expired - Fee Related CN1028867C (en) | 1989-03-01 | 1990-03-01 | Processes for preparing high-hard resin and polymerizable monomer |
| CN 94116268 Pending CN1104651A (en) | 1989-03-01 | 1994-09-22 | A glazing material comprising a high-hard transparent resin |
| CN 94116267 Pending CN1104650A (en) | 1989-03-01 | 1994-09-22 | A protective cover for display devices comprising a high-hard, transparent resin |
| CN 94116269 Pending CN1104631A (en) | 1989-03-01 | 1994-09-22 | A process for preparing a polymerizable monomer for a high-hard transparent resin |
Family Applications After (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94116268 Pending CN1104651A (en) | 1989-03-01 | 1994-09-22 | A glazing material comprising a high-hard transparent resin |
| CN 94116267 Pending CN1104650A (en) | 1989-03-01 | 1994-09-22 | A protective cover for display devices comprising a high-hard, transparent resin |
| CN 94116269 Pending CN1104631A (en) | 1989-03-01 | 1994-09-22 | A process for preparing a polymerizable monomer for a high-hard transparent resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (4) | CN1028867C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105859586A (en) * | 2016-04-15 | 2016-08-17 | 江苏利田科技股份有限公司 | 2-functionality-degree makrolon urethane acrylate and preparation method and application thereof |
| CN106711455A (en) * | 2016-11-28 | 2017-05-24 | 德阳九鼎智远知识产权运营有限公司 | Sulfurized amino polymer anode material and lithium ion battery prepared from thereof |
| CN109851754A (en) * | 2018-12-17 | 2019-06-07 | 山东益丰生化环保股份有限公司 | A kind of high refractive index polyurethane optical resin material, preparation method and optical element |
-
1990
- 1990-03-01 CN CN 90101780 patent/CN1028867C/en not_active Expired - Fee Related
-
1994
- 1994-09-22 CN CN 94116268 patent/CN1104651A/en active Pending
- 1994-09-22 CN CN 94116267 patent/CN1104650A/en active Pending
- 1994-09-22 CN CN 94116269 patent/CN1104631A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CN1104651A (en) | 1995-07-05 |
| CN1104650A (en) | 1995-07-05 |
| CN1104631A (en) | 1995-07-05 |
| CN1048392A (en) | 1991-01-09 |
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