CN101824120B - High heat resistance acrylic copolymer and preparation method thereof - Google Patents
High heat resistance acrylic copolymer and preparation method thereof Download PDFInfo
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- CN101824120B CN101824120B CN2009100079830A CN200910007983A CN101824120B CN 101824120 B CN101824120 B CN 101824120B CN 2009100079830 A CN2009100079830 A CN 2009100079830A CN 200910007983 A CN200910007983 A CN 200910007983A CN 101824120 B CN101824120 B CN 101824120B
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- heat resistance
- high heat
- methyl
- verivate
- acrylate monomer
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- 0 C1CC2C(C3)C(C4)C(C5C(CC6)CC6C55)C5C4*C3C2C1 Chemical compound C1CC2C(C3)C(C4)C(C5C(CC6)CC6C55)C5C4*C3C2C1 0.000 description 1
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Abstract
The invention provides a high heat resistance acrylic copolymer which comprises repetitive units of a monomer shown by a general formula (1) and repetitive units of a (methyl) acrylate monomer derivative, wherein x is equal to 1-3, and y is equal to 0-3. The acrylic copolymer has high heat resistance and low hydroscopicity.
Description
[technical field]
The present invention relates to a kind of polymkeric substance, particularly relate to a kind of acrylic acid esters co-polymer with high heat resistance and low water absorbable.
[background technology]
The optical grade acrylic polymer is the extremely wide material of purposes; Range of application comprises light guiding plate (light guiding plates; LGP), plasma display panel header board (PDP front plants), optical grade diffuser plate (optical diffusion plates) or optical disk materials (optical discs) etc., mainly be because due to its high light transmittance (high transparency), low birefringence (low birefringence) and the good weatherability properties (weatherresistance).Compare with other material, its low price is especially as one of indispensable characteristics of optical grade material.Yet as the optical grade material, acrylic polymer but still exists relatively low thermotolerance (heat resistance) and higher water-absorbent (water absorption).Therefore, how to improve above-mentioned shortcoming, just become important topic on the present industry.
Carrying out to low heat resistant that how to improve acrylic polymer and the existing considerable research of high-hydroscopicity.At first; For improving the thermotolerance aspect of PMMA, existing many methods are studied and develop, for example with MMA and the alpha-methyl styrene (copolymerization (U.S.Pat.No.3 of α-methylstyrene); 135; 723), with MMA and maleic anhydride (maleic anhydride) copolymerization (Japanese Laid-open Japanese Patent Examined Publication No.49-10156), or with MMA and maleimide (maleimide) copolymerization (JP-ANo.61-95011).In addition MMA and polyfunctional monomer are carried out copolymerzation with cross-linking reaction (Japanese Patent Unexamined Publication No.63-30510).And be reacted into the polymkeric substance (Japanese PatentUnexamined Publication No.61-64703) that contains methacrylic imide (methacrylimide-containing) with primary amine (primary amine) and methyl acrylic ester resin (methacrylic resin).Though aforesaid method can improve the thermotolerance of acrylic polymer, following, it is slow to produce for example copolyreaction speed, or multipolymer regular meeting has color, makes degradation problem under the transparence.
Aspect the reduction water-absorbent, for example carry out copolyreaction and obtain multipolymer (Japanese Patent ApplicationLaid-Open (JP-A) No.58-5318) or carry out copolyreaction to obtain multipolymer (JP-A No.58-13652) with MMA and methylacrylic acid benzyl ester (benzylmethacrylate) with MMA and cyclohexyl methacrylate (cyclohexylmethacrylate).Though the above-mentioned multipolymer that obtains has low water absorbable, its polymkeric substance thermotolerance is not good.Therefore, exploitation has high thermal stability, and the polymkeric substance of low water absorbable promptly becomes makes the target that optical grade macromolecule resin material institute desire is pursued.
[summary of the invention]
One of main points of the present invention are to provide a kind of high heat resistance acrylic copolymer.This acrylic acid esters co-polymer is made up of the monomeric repeating unit shown in the general formula (1) and the repeating unit of (methyl) acrylate monomer verivate:
X=1～3 wherein, y=0～3.
Another main points of the present invention are to provide a kind of preparation method of high heat resistance acrylic copolymer; Comprise: in the presence of initiators for polymerization; Alpha-substitution acrylate monomer verivate shown in the general formula (2) and (methyl) acrylate monomer verivate are carried out copolymerization, and wherein this initiators for polymerization is the superoxide with one or more O-O keys:
X=1～3 wherein, y=0～3.
High heat resistance acrylic copolymer of the present invention is made up of the monomeric repeating unit shown in the general formula (1) and the repeating unit of (methyl) acrylate monomer verivate basically.The present invention with superoxide with one or more O-O keys as initiators for polymerization; Alpha-substitution acrylate monomer verivate shown in the general formula (2) and (methyl) acrylate monomer verivate are carried out copolymerization; Alpha-substitution acrylate monomer verivate with general formula (2) can cause the cyclopolymerization reaction when polymerization, and forms the tetrahydropyrans ring structure.
For letting the present invention's above-mentioned purpose, characteristic and the advantage can be more obviously understandable, hereinafter is special lifts preferred embodiment, and cooperates appended graphicly, elaborates as follows:
[embodiment]
One of main points of the present invention are to provide a kind of high heat resistance acrylic copolymer.Acrylic acid esters co-polymer of the present invention is made up of the monomeric repeating unit shown in the general formula (1) and the repeating unit of (methyl) acrylate monomer verivate.
In general formula (1), x=1～3, y=0～3.
The number-average molecular weight of acrylic acid esters co-polymer of the present invention is substantially between 5,000～1, and 000,000, be preferably 50,000～10,00,000, be more preferred from 50,000～500,000.
Above-mentioned (methyl) acrylate monomer verivate can be by shown in the general formula (3).
In general formula (3), R
3Can be hydrogen or methyl.R
4Can be carbon number and be 1～22 alkyl or carbon number and be 5～22 naphthenic base, above-mentioned (methyl) acrylate monomer verivate is preferable selection with TEB 3K (methylmethacrylate), Jia Jibingxisuanyizhi (ethyl methacrylate), methylacrylic acid benzyl ester (benzylmethacrylate), methylacrylic acid cyclohexyl ester (cyclohexyl methacrylate) with methyl acrylate (methyl acrylate).
In the high heat-proof acrylic lipin polymer of the present invention, the molar percentage of the repeating unit of monomeric repeating unit shown in the general formula (1) and (methyl) acrylate monomer verivate is substantially between 5～95%.
Another main points of the present invention are to provide a kind of preparation method of high heat resistance acrylic copolymer; May further comprise the steps: in the presence of initiators for polymerization, the alpha-substitution acrylate monomer verivate shown in the general formula (2) and (methyl) acrylate monomer verivate are carried out copolymerization.Above-mentioned initiators for polymerization is the superoxide with one or more O-O keys.
In general formula (2), x=1～3, y=0～3.
Above-mentioned initiators for polymerization can be Lucidol (benzoyl peroxide; BPO), t-butyl peroxy-2-ethylhexanoate (tert-butylperoxy-2-ethylhexanate; PBO), ditertiary butyl peroxide (di-tert-butylperoxide; PBD), tert-butyl peroxy isopropyl carbonate (tert-butylperoxyisopropylcarbonate, PBI) or normal-butyl-4,4-two (tertiary butyl) valerate (n-butyl-4; 4-bis (tert-butylperoxy) valarate, PHV) etc.
Above-mentioned (methyl) acrylate monomer verivate can be by shown in the general formula (3).
In general formula (3), R
3Can be hydrogen or methyl.R
4Can be carbon number and be 1～22 alkyl or carbon number and be 5～22 naphthenic base.Above-mentioned (methyl) acrylate monomer verivate is preferable selection with TEB 3K (methylmethacrylate), Jia Jibingxisuanyizhi (ethyl methacrylate), methylacrylic acid benzyl ester (benzylmethacrylate), methylacrylic acid cyclohexyl ester (cyclohexyl methacrylate) with methyl acrylate (methyl acrylate).
The molar percentage of above-mentioned alpha-substitution acrylate monomer verivate is preferably 40～85% substantially between 95～5%, is more preferred from 30～85%.
High heat resistance multipolymer of the present invention can be through multiple known polymerization methods preparation, for example cationic polymerization, group transfer polymerization method (GTP) or radical polymerization.
In radical polymerization, be preferable selection so that use initiators for polymerization to carry out polyreaction with one or more O-O keys.Use this initiators for polymerization in shorter polymerization reaction time, to obtain higher yields, its consumption is 0.1～1% of a monomer weight.
The employed solvent of above-mentioned polyreaction can comprise the for example varsol of toluene, YLENE, benzene or hexane, for example the halogenated hydrocarbon solvent of chloroform, methylene dichloride or tetracol phenixin, THF, DMSO 99.8MIN., diethyl ether or its analogue.
High heat resistance acrylic copolymer of the present invention is made up of the monomeric repeating unit shown in the general formula (1) and the repeating unit of (methyl) acrylate monomer verivate basically.The present invention with superoxide with one or more O-O keys as initiators for polymerization; Alpha-substitution acrylate monomer verivate shown in the general formula (2) and (methyl) acrylate monomer verivate are carried out copolymerization; Alpha-substitution acrylate monomer verivate with general formula (2) can cause the cyclopolymerization reaction when polymerization, and forms the tetrahydropyrans ring structure.
In the embodiment of the invention, the molecular weight of acrylic acid esters co-polymer and MWD degree are to be standard specimen with PS (PS), by GPC method (solvent: THF) obtain.Second-order transition temperature (Tg) is recorded by DSC.
[embodiment]
[embodiment 1]
The preparation of acrylic ester monomer (TCDHM)
At first, the vinylformic acid 8-methylol three with 11.02 grams encircles [5.2.1.0
2,6] decyl ester (8-hydroxymethyltricyclo [5.2.1.0
2,6] decanyl acrylate, HMTCDA) (50mmol), 1.75 * 10
-2The Resorcinol (hydroquinone) (1.59 * 10 of gram
-4Mol), 1.50 the gram paraformaldehyde (paraformaldehyde) (50mmol), 0.75 the gram 1,4-diazabicyclo [2.2.2] octane (1,4-diazabicyclo [2.2.2] octane, DABCO) (6.63 * 10
-3Mol, white solid) mixes with 3.83 milliliters the trimethyl carbinol (tert-butanol) (40mmol, colourless liquid), place 100 milliliters of reaction flasks, in 80 ℃ of reactions 5 days down.After waiting to remove solvent; Carry out separation and purification (elutriant be normal hexane/ether=10: 1) with silica gel column chromatography; Can obtain colorless liquid product vinylformic acid three ring decyl-α-(methylol) esters (acrylate of tricyclodecanyl-α-(hydroxymethyl) of 6.52 grams; TCDHM), productive rate is 54%.
[embodiment 2]
The preparation of acrylic acid esters co-polymer (Mn=63,000)
At first, with the TCDHM (prepared) of 0.48 gram by embodiment 1 (1mmol), 0.96 milliliter methyl acrylate (MMA) (9mmol), 5.67 milligrams BPO (2.34 * 10
-2Mmol) mix with 2 milliliters toluene (toluene), place 50 milliliters of reaction flasks.Under nitrogen environment, solution is warming up to 80 ℃ of reactions 1.5 hours.After question response finishes, add 50 milliliters methyl alcohol, can obtain a large amount of white solid depositions.After the filtration, carry out redeposition (THF/methyl alcohol=1: 6) with 10 milliliters THFs (THF) dissolving and with methyl alcohol.After treating repeatedly 3 times, product is drained, can be obtained the white solid product of 1.19 grams, productive rate is 86%.The number-average molecular weight of multipolymer is 63,000, and MWD degree (PDI) is 1.84, and second-order transition temperature (Tg) is 114 ℃, shown in table one.
[embodiment 3]
The preparation of acrylic acid esters co-polymer (Mn=80,400)
At first, with the TCDHM (prepared) of 0.96 gram by embodiment 1 (2mmol), 0.85 milliliter MMA (8mmol), 5.67 milligrams BPO (2.34 * 10
-2Mmol) mix with 2 milliliters toluene (toluene), place 50 milliliters reaction flask.Under nitrogen environment, solution is warming up to 80 ℃ of reactions 1.5 hours.After question response finishes, add 50 milliliters methyl alcohol, can obtain a large amount of white solid depositions.After to be filtered, carry out redeposition (THF/methyl alcohol=1: 6) with 10 milliliters THFs (THF) dissolving and with methyl alcohol.After treating repeatedly 3 times, product is drained, can be obtained the white solid product of 1.58 grams, productive rate is 90%.The number-average molecular weight of multipolymer is 80,400, and MWD degree (PDI) is 1.73, and second-order transition temperature (Tg) is 125 ℃, shown in table one.
[comparing embodiment 1]
The preparation of acrylic polymer (PMMA) (Mn=106,300)
At first, with the MMA (10mmol) of 1 gram, 5.67 milligrams BPO (3.90 * 10
-2Mmol) mix with 2 milliliters toluene (toluene), place 50 milliliters reaction flask, under nitrogen environment, solution is warming up to 80 ℃ of reactions 1.5 hours.After question response finishes, add 50 milliliters methyl alcohol, can obtain a large amount of white solid depositions.After to be filtered, carry out redeposition (THF/methyl alcohol=1: 6) with 10 milliliters THFs (THF) dissolving and with methyl alcohol.After treating repeatedly 3 times, product is drained, can be obtained the white solid product of 0.85 gram, productive rate is 85%.The number-average molecular weight of PMMA polymkeric substance is 106,300, and MWD degree (PDI) is 1.14, and second-order transition temperature (Tg) is 105 ℃, shown in table one.
Table one
Can find out the acrylic acid esters co-polymer (embodiment 2～3) of the present invention's preparation, PMMA acrylic polymer (comparing embodiment 1) height that its second-order transition temperature all prepares than convention by table one.This representes that promptly the PMMA-co-TCDHM acrylic acid esters co-polymer of the present invention's preparation has preferable thermostability with respect to the PMMA acrylic polymer of prior art for preparing.
Though the present invention discloses as above with preferred embodiment; Right its is not that any those skilled in the art are in spirit that does not break away from the present invention and scope in order to qualification the present invention; When can doing to change and retouching, so protection scope of the present invention is as the criterion when looking the accompanying claims person of defining.
Claims (8)
1. the acrylic acid esters co-polymer of a high heat resistance, it is made up of monomeric repeating unit shown in the general formula (1) and repeating unit of (methyl) acrylate monomer verivate:
X=1～3 wherein, y=0～3.
2. high heat resistance acrylic copolymer as claimed in claim 1, wherein the number-average molecular weight of this acrylic acid esters co-polymer is 5,000 to 1,000,000.
3. high heat resistance acrylic copolymer as claimed in claim 1, wherein be somebody's turn to do (methyl) acrylate monomer verivate by shown in the general formula (3):
R wherein
3Be hydrogen or methyl, R
4For carbon number is that 1～22 alkyl or carbon number are 5～22 naphthenic base.
4. high heat resistance acrylic copolymer as claimed in claim 1, wherein the molar percentage of the repeating unit of monomeric repeating unit shown in this general formula (1) and this (methyl) acrylate monomer verivate is between 5～95%.
5. the preparation method of a high heat resistance acrylic copolymer; Comprise: in the presence of initiators for polymerization; Alpha-substitution acrylate monomer verivate shown in the general formula (2) and (methyl) acrylate monomer verivate are carried out copolymerization, and wherein this initiators for polymerization is the superoxide with one or more O-O keys:
X=1～3 wherein, y=0～3.
6. the preparation method of high heat resistance acrylic copolymer as claimed in claim 5; Wherein this initiators for polymerization is Lucidol (benzoyl peroxide; BPO), t-butyl peroxy-2-ethylhexanoate (tert-butylperoxy-2-ethylhexanate, PBO), ditertiary butyl peroxide (di-tert-butylperoxide, PBD), tert-butyl peroxy isopropyl carbonate (tert-butylperoxyisopropylcarbonate; PBI) or normal-butyl-4; 4-two (t-butyl peroxy) valerate (n-butyl-4,4-bis (tert-butylperoxy) valarate, PHV).
7. the preparation method of high heat resistance acrylic polymers as claimed in claim 5, wherein be somebody's turn to do (methyl) acrylate monomer verivate by shown in the general formula (3):
R wherein
3Be hydrogen or methyl, R
4For carbon number is that 1～22 alkyl or carbon number are 5～22 naphthenic base.
8. the preparation method of high heat resistance acrylic copolymer as claimed in claim 5, wherein the molar percentage of this alpha-substitution acrylate monomer verivate is between 95～5%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009100079830A CN101824120B (en) | 2009-03-06 | 2009-03-06 | High heat resistance acrylic copolymer and preparation method thereof |
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| CN2009100079830A CN101824120B (en) | 2009-03-06 | 2009-03-06 | High heat resistance acrylic copolymer and preparation method thereof |
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| CN101824120B true CN101824120B (en) | 2012-05-23 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1238787A (en) * | 1996-10-29 | 1999-12-15 | 三菱丽阳株式会社 | Lowly birefringent polymer, process for the preparation thereof, and optical pickup lens |
| CN1582308A (en) * | 2001-11-07 | 2005-02-16 | 大曹株式会社 | Solidified composition excellent in optical characteristics |
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2009
- 2009-03-06 CN CN2009100079830A patent/CN101824120B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1238787A (en) * | 1996-10-29 | 1999-12-15 | 三菱丽阳株式会社 | Lowly birefringent polymer, process for the preparation thereof, and optical pickup lens |
| CN1582308A (en) * | 2001-11-07 | 2005-02-16 | 大曹株式会社 | Solidified composition excellent in optical characteristics |
Non-Patent Citations (2)
| Title |
|---|
| JP平10-295237A 1998.11.10 |
| 蒋硕键等.（甲基）丙烯酸多脂环酯及其聚合物.《石油化工》.1995,(第9期),第657-668页. * |
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