CN1210869A - Method for producing heat-resistant copolymerized resin - Google Patents
Method for producing heat-resistant copolymerized resin Download PDFInfo
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- CN1210869A CN1210869A CN 97106095 CN97106095A CN1210869A CN 1210869 A CN1210869 A CN 1210869A CN 97106095 CN97106095 CN 97106095 CN 97106095 A CN97106095 A CN 97106095A CN 1210869 A CN1210869 A CN 1210869A
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Abstract
The present invention uses suspending polymerization process.Technologically, it features that in the presence of initiator the reaction temperature is controlled first in 45-60 deg.c during the first stage and then raised to 70-80 deg.c after reaching reaction conversion rate of 50% to proceed the reaction completely. The initiator accounts for 0.5-3% of total monomer, and the copolymerized monomers may be maleimide, aromatic olefines, acrylates and other polymerizable monomer. The present invention has stable reaction system and easy-to-realize technical design. The residual amount of all monomer is below 1%, and that of maleimide is below 0.5%.
Description
The invention belongs to a kind of manufacture method of heat-resistant copolymerized resin, heat-resistant copolymerized resin is used in the heat-proof modifier of PVC plastics especially.
PVC is a kind of broad-spectrum general-purpose plastics, can be different by adding various auxiliary agents and using various forming methods to make performance, and broad-spectrum soft or hard plastics.But the PVC goods have three big shortcomings usually, and first impact-resistance is poor; Second poor processability, the melt temperature height of polyvinyl chloride resin is 210 ℃, but the poor heat stability of PVC, 100 ℃ just begin to decompose, because the processing of PVC mostly will be carried out under molten state, and the processing solution viscosity height of PVC, mobile poor, when calendering and extruded product, bubble often appears, solution breaks, and causes quality of item to descend; The 3rd is that PVC goods heat-drawn wire is too low, and Vicat softening point is only about 90 ℃.
For performance and its use range of expansion of improving PVC, initial people often use some small molecules softening agent, but these small molecules softening agent stripping take place, volatilization and migration in the processing of goods and application process, contaminate environment not only also makes goods hardening deliquescing simultaneously and loses use value.So people come modified PVC with high polymer, developed various PVC auxiliary agents in succession, as: MBS, CPE, ACR, ABS etc., these properties-correcting agent have solved the impact-resistance of PVC and the problem of processibility substantially.In order to improve the thermotolerance of PVC, can adopt the method for blend, with the method for blend improve PVC thermotolerance, requiring has intermiscibility as well as possible and high as far as possible vicat softening temperature between properties-correcting agent and the PVC, must have simultaneously alap melt temperature and solution viscosity again, therefore be fit to do the polymkeric substance of PVC heat-proof modifier and few, what be widely used now is N-substituted maleimide amine copolymer thing.Initial people use alpha-methyl styrene, methyl methacrylate, and the ABS blend of terpolymer of acrylonitrile and PVC and methacrylic acid modification can improve the thermotolerance of PVC, but stable on heating improvement is limited to this method to PVC.Therefore people have developed N-substituted maleimide amine again, methyl methacrylate, cinnamic copolymer resins comes PVC is carried out heat resistance modified, and this class PVC heat-proof modifier modified resins not only has higher thermotolerance but also have good mechanical performance and processing characteristics.Manufacturing technology as this maleimide copolymer adopts solution polymerization, letex polymerization and suspension polymerization.Solution polymerization, emulsion polymerization aftertreatment be difficulty relatively, is difficult to realize industrialization, so maleimide is synthetic based on suspension method.But adopt suspension method because the copolyreaction speed of maleimide is very fast in initial reaction stage, the system rather unstable, sudden and violent poly-phenomenon easily takes place, therefore for the stability of guarantee system, the consumption of general initiator is very low, be not higher than 0.5% of monomer total amount, like this because the consumption of initiator is low, and the difference of the polymerization rate of each copolymerization component, make the amount of residual monomer in the maleimide copolymer resins than higher, because the boiling point of maleimide is very high, adopt the also very difficult content that reduces the maleimide in the resin of mode of decompression ash disposal simultaneously, the existence of monomer maleimide has had a strong impact on the resistance toheat of maleimide copolymer resins.In order to reduce the content of maleimide monomer in the resin, flat 3-188111 patent disclosure a kind of method that can adopt composite initiator.The initiator that uses in this method is made up of two kinds of different initiators of cracking temperature, a kind of transformation period of initiator is that 10 hours cracking temperature is between 60～74 ℃, consumption is 0.01～1%, the another kind of transformation period be 10 hours cracking temperature between 95～115 ℃, consumption is 0.001～0.5%.Under 60～90 ℃, begin reaction, improve temperature of reaction to 100～130 ℃ in the reaction later stage, under the effect of high-temperature initiator, remaining monomer consumption is fallen, and to obtain the few copolymer resins of residual monomer content, still the use temperature owing to high-temperature initiator reaches more than 100 ℃, under such temperature, react, make that the design of reactor is more complicated, temperature controlling is also more difficult, is unfavorable for industrializing implementation.
It is few to the purpose of this invention is to provide a kind of residual monomer amount that makes, and reaction system is steady, is easy to the manufacture method of the heat-resistant copolymerized resin of industrializing implementation.
Technical scheme of the present invention is to adopt suspension polymerization, the major technique characteristics are that comonomer is under initiator, initial stage control reaction temperature in reaction is 45～60 ℃, and reaction conversion ratio improves temperature of reaction to 70～80 and ℃ continues to react completely after 50%.
Above-mentioned this low temperature begins reaction, and the mode of high temperature polymerization can guarantee the stability of reaction system, and maximum temperature also is no more than 100 ℃, and technological design is more conducive to industrializing implementation.Reaction conversion ratio surpasses 50%, is to make the viscosity of reaction soln reduce later on intensification again, at high temperature makes to react completely.Being preferably in reaction conversion ratio reaches at 50～75% o'clock and heats up.The amount of used initiator can be 0.5～3% of monomer total amount, is guaranteeing the down stable of reaction system, and speed of response is accelerated, and the residual monomer amount of gained resin reduces.The optimum quantum of utilization of initiator is 1～2.5%.The amount of initiator is if be lower than 0.5%, and then residual single amount can not reduce in the resin, if it is not steady to be higher than 3% anti-strained, and the mechanical property of gained resin will reduce.Initiator adopts between 60～74 ℃ any of 10 hour transformation period decomposition temperature, as: Diisopropyl azodicarboxylate, be called for short AIBN; Benzoyl peroxide is called for short BPO.
The comonomer of copolymer resins is a maleimide, fragrant olefines, esters of acrylic acid and the monomeric multiple copolymer of other polymerizabilities.Concrete a kind of is the maleimide of 5～40Wt%, the multiple copolymer of one or both compositions in the atomatic olefins of 10～50Wt% and esters of acrylic acid, the vinyl cyanide.If do not have monomer esters of acrylic acid, the amount of vinyl cyanide is 5～40Wt%; If there is not the monomer vinyl cyanide, the amount of esters of acrylic acid is for being 10～50Wt%; If monomer vinyl cyanide and esters of acrylic acid all exist, their amount is vinyl cyanide 5～40Wt%, esters of acrylic acid 10～50Wt%.
Maleimide is preferably N-phenyl substituted maleimide amine or N-cyclohexyl substituted maleimide amine, and molecular formula can be represented with following formula respectively:
R1 wherein, R2, R3 can be the alkyl of H or C1-C4, straight or branched all can.Its optimum amount is 10～30%.
Atomatic olefins is taken from wherein one or both, can be vinylbenzene, alpha-methyl styrene; Esters of acrylic acid is a kind of in methyl methacrylate, Jia Jibingxisuanyizhi, the butyl methacrylate.
Concrete grammar is: the initiator that adds 0.5～3 part in 100 parts in the monomeric mixture of polymerizability, suspension polymerization in polyvinyl alcohol water solution, under 45～60 ℃, carried out initiation reaction 1～2 hour, be warming up to 70～80 ℃ of reactions 8～10 hours again, after centrifugal, washing, drying, obtain rosin products.
The best of the present invention is the terpolymer of N-phenyl substituted maleimide amine, vinylbenzene, methyl methacrylate, in the heat-resistant copolymerized resin that obtains, residual single amount of N-phenyl substituted maleimide amine is below 0.5%, residual single amount of methyl methacrylate is below 0.2%, and cinnamic residual single amount is below 0.1.
The transformation period of initiator is measured with following currently known methods:
A certain amount of initiator is dissolved in (benzene, toluene) in the certain amount of solvent, in the Glass tubing of replacing with N2 of packing into then, the sealing back make its decomposition under the fixed temperature.
The decomposition amount of initiator is X (moL/dm
3), initial stage concentration is a (mol/dm
3), the decomposition rate constant is k (h
-1), the time is t (h).
The speed mode of decomposition reaction can be expressed as follows like this:
Dx/dt=K (a-x) is 1na/a-x=Kt
Here suppose that when certain temperature the transformation period of initiator is H (h), then: during t=H, so x=a/2 is KH=1n2 ... (1) here: k=AExp (E/RT) ... (2), E is activation energy (Kcal/mol); A is a frequency factor; R is a gas law constant; T is a temperature.So can obtain from (1), (2) two formulas:
1nH=E/RT-1nA, because 1nH and 1/T are linear relations, the H when measuring differing temps T can obtain the straight line of 1nH and 1/T, the decomposition temperature in the time of can being 10h in the hope of half-lives of initiators thus.
Advantage of the present invention: use present method reaction system steady, production engineering specifications is low, be easy to industrializing implementation, institute's synthetic heat-resistant copolymerized resin is under the prerequisite that keeps other performance, the monomer residual volume is low, all monomeric residual volumes are below 1%, and wherein the residual volume of maleimide is below 0.5%.Heat-resistant copolymerized resin of the present invention also is a kind of engineering plastics of excellent property.
Embodiment 1:
In the polymeric kettle that stirring, condenser and sheathed heater are housed, add water earlier by following prescription, open stirring and be warming up to 45 ℃ and adjust mixing speed 200～500RPM, add oil phase by proportioning.45 ℃ were reacted 2 hours, were warming up to 60 ℃ of reactions 1 hour, and this moment, transformation efficiency was 69%, were warming up to 80 ℃ of reactions 8 hours again, stopped reaction.Centrifugal, washing, after dry, promptly obtain resin of the present invention.
Water:
400 parts in water
0.6 part of polyvinyl alcohol (in water)
Dispersion aids vinylbenzene one maleic anhydride 300ppm (in water)
Oil phase:
30 parts of N-phenyl substituted maleimide amine
25 parts of methyl methacrylates
45 parts of vinylbenzene
2 parts of BPO
The processing test:
The yield of heat-resistant resin of the present invention is measured with weighting method, the monomer residual volume is measured with vapor-phase chromatography, with following each component according to a conventional method under 185 ℃ in opening on the refining formula mixing roll mixing 3 minutes, then under 185 ℃, compacting is 5 minutes on the compression molding instrument, makes the print of 3 mm thick:
70 parts of PVC (TK800)
30 parts of heat-resistant resins of the present invention
0.5 part of lubricant G-74 (commercially available)
3 parts of stablizers 890 (commercially available)
Press the Vicat softening point that the GB1633-79 method is measured print, the results are shown in Table 1.
Embodiment 2:
Among the embodiment 1, maleimide changes 35 parts into, and vinylbenzene changes 40 parts into, and methyl methacrylate is constant, and all the other are with embodiment 1.
Comparative example 1:
Among the embodiment 1, the starting polymerization temperature is 65 ℃, and all the other are with embodiment 1.
Comparative example 2:
Among the embodiment 1, BPO changes 0.4 part into, and all the other are with embodiment 1.
Table 1:
| Test number | Vicat softening point (℃) | Monomer conversion (%) | Apparent density (g/ml) | Mobile (s) |
| Embodiment 1 | ?108.4 | ????99.6 | ?0.562 | ????6.86 |
| Embodiment 2 | ?110.2 | ????99.2 | ?0.578 | ????5.98 |
| Comparative example 1 | ??-- | Sudden and violent poly- | ??-- | ?????-- |
| Comparative example 2 | ?108.7 | ????76.4 | ?0.584 | ????7.32 |
Following examples 3～11 are carried out suspension polymerization by embodiment 1 method, and wherein water is constant.
Embodiment 3:
5 parts of maleimides, 10 parts of methyl methacrylates, 50 parts of vinylbenzene, 35 parts of vinyl cyanide, 0.8 part of BPO, monomer conversion 99.1%.Transformation efficiency is 66% before being warming up to 80 ℃.
Embodiment 4:
10 parts of maleimides, 50 parts of methyl methacrylates, 40 parts of vinylbenzene, BPO1 part, monomer conversion 99.2%.Transformation efficiency is 74.2 before being warming up to 80 ℃.
Embodiment 5:
15 parts of maleimides, 20 parts of methyl methacrylates, 45 parts of vinylbenzene, 20 parts of alpha-methyl styrenes, 3 parts of BPO, monomer conversion 99.7%.Transformation efficiency is 68.5% before being warming up to 80 ℃.
Embodiment 6:
20 parts of maleimides, 35 parts of vinylbenzene, 30 parts of alpha-methyl styrenes, 15 parts of vinyl cyanide, 2 parts of BPO, monomer conversion 99.6%.
Embodiment 7:
30 parts of maleimides, 25 parts of methyl methacrylates, 45 parts of vinylbenzene, 1.9 parts of BPO, monomer conversion 99.6%.
Embodiment 8:
20 parts of maleimides, 40 parts of Jia Jibingxisuanyizhis, 30 parts of vinylbenzene, 10 parts of vinyl cyanide, 1.5 parts of BPO.
Embodiment 9:
30 parts of maleimides, 30 parts of butyl methacrylate, 20 parts of vinylbenzene, 2 parts of BPO.
Embodiment 10:
50 parts of maleimides, 20 parts of methyl methacrylates, 10 parts of vinylbenzene, 15 parts of alpha-methyl styrenes, AIBN2.5 part.
Embodiment 11:
5 parts of maleimides, 10 parts of methyl methacrylates, 50 parts of vinylbenzene, 35 parts of vinyl cyanide, 0.5 part of BPO, monomer conversion 93.4%.Transformation efficiency is 66% before being warming up to 80 ℃.
Claims (10)
1, the preparation method of heat-resistant copolymerized resin, adopting suspension polymerization, it is characterized in that comonomer under initiator, is 45～60 ℃ in the initial stage control reaction temperature of reacting, reaction conversion ratio improves temperature of reaction to 70～80 and ℃ continues to react completely after 50%.
2, method according to claim 1 is characterised in that reaction conversion ratio reaches 50%～75%, improves temperature of reaction to 70～80 and ℃ continues to react completely.
3, method according to claim 1 is characterised in that initiator is that 10 hour transformation period decomposition temperature is any between 60～74 ℃.
4, method according to claim 1, the amount that is characterised in that initiator is 0.5～3Wt% of copolymer resins monomer total amount.
5, method according to claim 4 is characterised in that amount the best of initiator is 1～2.5Wt% of copolymer resins monomer total amount.
6,, be characterised in that copolymer resins is the maleimide by 5～50Wt%, the multiple copolymer of one or both compositions in the atomatic olefins of 10～65Wt% and esters of acrylic acid, the vinyl cyanide according to claim 1,4 described methods.
7, method according to claim 6 is characterised in that copolymer resins is the maleimide by 5～50Wt%, the multipolymer that the atomatic olefins of 10～65Wt% and the esters of acrylic acid of 10～50Wt% are formed.
8, method according to claim 6 is characterised in that copolymer resins is the maleimide by 5～50Wt%, the multipolymer that the atomatic olefins of 10～65Wt% and the vinyl cyanide of 5～40Wt% are formed.
9, method according to claim 6 is characterised in that copolymer resins is the maleimide by 5～50Wt%, the atomatic olefins of 10～65Wt%, the multipolymer that the vinyl cyanide of 5～40Wt% and the esters of acrylic acid of 10～50Wt% are formed.
10, method according to claim 6, be characterised in that maleimide can be a kind of in N-phenyl substituted maleimide amine, the N-cyclohexyl substituted maleimide amine, atomatic olefins is selected from vinylbenzene, alpha-methyl styrene, and esters of acrylic acid can be methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106095A CN1081648C (en) | 1997-09-10 | 1997-09-10 | Method for producing heat-resistant copolymerized resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106095A CN1081648C (en) | 1997-09-10 | 1997-09-10 | Method for producing heat-resistant copolymerized resin |
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| Publication Number | Publication Date |
|---|---|
| CN1210869A true CN1210869A (en) | 1999-03-17 |
| CN1081648C CN1081648C (en) | 2002-03-27 |
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ID=5168368
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97106095A Expired - Fee Related CN1081648C (en) | 1997-09-10 | 1997-09-10 | Method for producing heat-resistant copolymerized resin |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059221A (en) * | 2013-01-22 | 2013-04-24 | 上海华谊（集团）公司 | Method for preparing high-performance maleimide copolymer by using suspension method |
| CN108055849A (en) * | 2015-07-03 | 2018-05-18 | 株式会社Lg化学 | The preparation method of vinyl chloride copolymer and the vinyl chloride copolymer prepared by the preparation method |
| CN116814024A (en) * | 2023-06-29 | 2023-09-29 | 扬州市岩特户外装备科技有限公司 | Resin composite material and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0699492B2 (en) * | 1984-06-05 | 1994-12-07 | 日本合成ゴム株式会社 | Method for manufacturing heat resistant resin |
| JPH0796580B2 (en) * | 1985-06-03 | 1995-10-18 | 三井東圧化学株式会社 | Transparent heat resistant styrene copolymer |
| CN1024348C (en) * | 1990-05-23 | 1994-04-27 | 孟凡彬 | Process for extraction of sweet stevia by ordinary resin |
-
1997
- 1997-09-10 CN CN97106095A patent/CN1081648C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059221A (en) * | 2013-01-22 | 2013-04-24 | 上海华谊（集团）公司 | Method for preparing high-performance maleimide copolymer by using suspension method |
| CN108055849A (en) * | 2015-07-03 | 2018-05-18 | 株式会社Lg化学 | The preparation method of vinyl chloride copolymer and the vinyl chloride copolymer prepared by the preparation method |
| CN108055849B (en) * | 2015-07-03 | 2020-09-08 | 株式会社Lg化学 | Method for preparing vinyl chloride copolymer and vinyl chloride copolymer prepared by the same |
| CN116814024A (en) * | 2023-06-29 | 2023-09-29 | 扬州市岩特户外装备科技有限公司 | Resin composite material and preparation method thereof |
| CN116814024B (en) * | 2023-06-29 | 2023-12-15 | 扬州市岩特户外装备科技有限公司 | Resin composite material and preparation method thereof |
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|---|---|
| CN1081648C (en) | 2002-03-27 |
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