CN105111359B - A kind of preparation method of polymethyl methacrylate copolymer - Google Patents
A kind of preparation method of polymethyl methacrylate copolymer Download PDFInfo
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Abstract
The present invention provides a kind of preparation methods of polymethyl methacrylate copolymer, using ontology or the method for polymerisation in solution.Using methyl methacrylate as the first monomer of monomer, methacrylic acid isoborneol rouge or isobomyl acrylate rouge introduce Third monomer as second comonomer, such as styrene, methyl acrylate, methacrylic acid and Methacrylamide.Using the glass transition temperature T of the obtained polymethylacrylic acid acid methyl terpolymer of the method for polymerisation in solutiongUp to 150.9 DEG C, thermal decomposition temperature T is originateddUp to 300.4 DEG C, while the water absorption rate of copolymer is only 0.33%.Using the glass transition temperature T of the obtained polymethylacrylic acid acid methyl terpolymer of the method for bulk polymerizationgUp to 149.6 DEG C, thermal decomposition temperature T is originateddUp to 292.9 DEG C, while the water absorption rate of copolymer is only 0.33%.This shows whether bulk polymerization or polymerisation in solution, and method of the invention can synthesize heat resistance, better heat stability and the low copolymer of water absorption rate.
Description
Technical field
The invention belongs to high molecular material preparation method fields, and in particular to a kind of polymethylacrylic acid acid methyl terpolymer
Preparation method.
Background technique
Polymethylacrylic acid acid methyl esters (PMMA) is a kind of transparent thermoplastic material.Its excellent optical characteristics, it is weather-proof
Property, chemical stability, the performances such as workability and physical mechanical property make it in aviation, automobile, illumination, electronics, optics instrument
The fields such as device and medical instrument are widely used.Although PMMA has above-mentioned excellent performance, it uses temperature
Low, the disadvantages of poor heat resistance, greatly limits its application range.Therefore, the heat resistance for improving PMMA widens its application field
Always popular research topic.
PMMA is a kind of line style amorphous polymers material, and glass transition temperature temperature is lower, is chained for its molecule
The characteristics of structure, for the discovery of some scientists by copolymerization large volume, the monomer with cyclic structure improves the resistance to of PMMA resin
Hot is a kind of highly effective method.Common approach has: MMA and maleic anhydride (MAn), the rings such as N- substituted maleimide amine
The monomer of shape structure is copolymerized, to introduce five-membered ring on PMMA main chain.MMA and maleic anhydride, gained copolymer
Heat resistance significantly improves, and mechanical property does not decline substantially, but copolymer water imbibition is larger, and cannot connect with water in polymerization process
Touching, otherwise maleic anhydride meeting partial hydrolysis, makes polymer performance decline (see plastics, 1999,28:4-18, Yang Ruiqin etc.).Use N-
Substituted maleimide amine and MMA are copolymerized, although the above problem is not present, the monomer of residual in the polymer is easy using
During heat-tinting (see JournalofAppliedPolymerScience, 1997,63:363-368, YuichiK etc.).
Summary of the invention
It is poor in order to solve PMMA resin heat resistance existing for prior art, thermal stability difference and the higher problem of water absorption rate.
The present invention provides a kind of preparation methods of polymethyl methacrylate copolymer, using bulk polymerization or solution
The method of polymerization.
Using the preparation method of polymerisation in solution, step and condition are as follows:
(1) according to weight, monomer I: monomer II: monomer III: solvent: initiator: chain-transferring agent is 70 ~ 90 parts:
8 ~ 20 parts: 2 ~ 10 parts: 30 parts: 1 × 10-5~1×10-4Part: 1 × 10-5~4×10-4Part；The monomer I is methyl methacrylate
Ester；The monomer II is selected from methacrylic acid isoborneol rouge or isobomyl acrylate rouge；The monomer III is selected from benzene second
Alkene, methyl acrylate, methacrylic acid or Methacrylamide；The initiator is selected from azo-bis-iso-dimethyl
(AIBME), azodiisobutyronitrile (AIBN), benzoyl peroxide (BPO) or di-t-butyl peroxide (DTBP)；The chain turns
It moves agent and is selected from n-octyl mercaptan (NOM) or tert-dodecylmercaotan (TDDM)；The solvent is selected from toluene or dimethylbenzene.
(2) according to said ratio, by monomer I, monomer II, monomer III, solvent, initiator and chain-transferring agent are added heat-resisting
Guan Zhong is configured to mixed solution, then, heat-resistant tube is placed on heating magnetic agitator and heats polymerization, polymerization temperature is
100 ~ 160 DEG C, polymerization reaction time is 3 ~ 6 hours；
(3) purification process: taking the mixed solution of above-mentioned preparation to pour into chloroform and make it dissolve, then will again together
It pours into anhydrous methanol and stirs, obtain white flocculent polymer, filter, washing, then filter, it is small that solids is spontaneously dried 12
Shi Hou is put into drying 24 hours in vacuum drying oven, obtains object.Polymer yield is 60 ~ 90%.
Using the preparation method of bulk polymerization, step and condition are as follows:
(1) other than not solubilizer, monomer I, monomer II, monomer III, solvent, initiator and chain-transferring agent, step and
Condition and the preparation method of use polymerisation in solution are all the same.
The utility model has the advantages that the method that the present invention uses bulk polymerization, using methyl methacrylate as the first monomer of monomer, methyl
Isobomyl acrylate rouge or isobomyl acrylate rouge introduce Third monomer as second comonomer, such as styrene, acrylic acid first
Ester, methacrylic acid and Methacrylamide.Using the obtained polymethylacrylic acid acid methyl esters copolymerization of the method for polymerisation in solution
The glass transition temperature T of objectgUp to 150.9 DEG C, thermal decomposition temperature T is originateddUp to 300.4 DEG C, while the water absorption rate of copolymer
Only 0.33%.Using the glass transition temperature T of the obtained polymethylacrylic acid acid methyl terpolymer of the method for bulk polymerizationg
Up to 149.6 DEG C, thermal decomposition temperature T is originateddUp to 292.9 DEG C, while the water absorption rate of copolymer is only 0.33%.This shows not
By being bulk polymerization or polymerisation in solution, method of the invention can synthesize heat resistance, better heat stability and water absorption rate
Low copolymer.
Detailed description of the invention
Fig. 1 is the DSC curve of polymethyl methacrylate terpolymer, wherein (a) embodiment 13；(b) embodiment 16；
(c) embodiment 22；(d) embodiment 19.
Fig. 2 is the TGA curve of polymethyl methacrylate copolymer, (a) embodiment 19；(b) embodiment 16；(c) real
Apply example 13；(d) embodiment 22.
Fig. 3 is the DSC curve that ontology and solution polymerization process synthesis is respectively adopted, wherein (a) embodiment 3；(b) embodiment
13。
Fig. 4 is the TGA curve that ontology and solution polymerization process synthesis is respectively adopted, wherein (a) embodiment 3；(b) embodiment
13。
Specific embodiment
The method that embodiment 1 uses polymerisation in solution.By the methyl methacrylate of 90 parts by weight, the acrylic acid of 8 parts by weight
Isoborneol rouge, the Methacrylamide of 2 parts by weight, 1 × 10-4The initiator A IBME of parts by weight, 2 × 10-4The TDDM of parts by weight
And 30 the toluene of parts by weight pour into the heat-resistant tube of 38mL, be configured to mixed solution.Then heat-resistant tube is placed on heated type
It is heated on magnetic stirring apparatus.Polymerization temperature is 100 DEG C, and polymerization time is 4 hours, obtains the solution of terpolymer；
(3) purification process: taking the mixed solution of above-mentioned preparation to pour into chloroform and make it dissolve, then will again together
It pours into anhydrous methanol and stirs, obtain white flocculent polymer, filter, washing, then filter, it is small that solids is spontaneously dried 12
Shi Hou is put into drying 24 hours in vacuum drying oven, obtains object.Polymer yield is 63%.
Embodiment 2 is by the methyl methacrylate of 70 parts by weight, 24 parts by weight (isobomyl acrylate rouge, 6 parts by weight
Methacrylamide, 2 × 10-4The initiator B PO of parts by weight, 4 × 10-4The dimethylbenzene of the TDDM of parts by weight and 30 parts by weight
It pours into the heat-resistant tube of 38mL, is configured to mixed solution.Then heat-resistant tube is placed on heating magnetic agitator and is heated.It is poly-
Closing temperature is 130 DEG C, and polymerization time is 4 hours, obtains the solution of terpolymer；Purification process while example 1.Polymer is received
Rate is 60%.
Embodiment 3 is by the methyl methacrylate of 80 parts by weight, the isobomyl acrylate rouge of 14 parts by weight, 6 parts by weight
Methacrylamide, 2 × 10-4The initiator DTBP of parts by weight, 4 × 10-4The TDDM of parts by weight and the toluene of 30 parts by weight fall
Enter in the heat-resistant tube of 38mL, is configured to mixed solution.Then heat-resistant tube is placed on heating magnetic agitator and is heated.Polymerization
Temperature is 130 DEG C, and polymerization time is 4 hours, obtains the solution of terpolymer；Purification process while example 1.Polymer yield
It is 62%.
Embodiment 4 by the methyl methacrylate of 90 parts by weight, the isobomyl acrylate rouge of 6 parts by weight, 4 parts by weight first
Base acrylic acid, 2 × 10-4The initiator DTBP of parts by weight, 4 × 10-4The TDDM of parts by weight and the toluene of 30 parts by weight pour into
In the heat-resistant tube of 38mL, it is configured to mixed solution.Then heat-resistant tube is placed on heating magnetic agitator and is heated.Polymerization temperature
Degree is 150 DEG C, and polymerization time is 3.5 hours, obtains the solution of terpolymer；Purification process while example 1.Polymer yield
It is 61%.
Embodiment 5 is by the methyl methacrylate of 80 parts by weight, the isobomyl acrylate rouge of 16 parts by weight, 4 parts by weight
Methacrylic acid, 2 × 10-4The initiator A IBN of parts by weight, 4 × 10-4The TDDM of parts by weight and the dimethylbenzene of 30 parts by weight fall
Enter in the heat-resistant tube of 38mL, is configured to mixed solution.Then heat-resistant tube is placed on heating magnetic agitator and is heated.Polymerization
Temperature is 100 DEG C, and polymerization time is 4 hours, obtains the solution of terpolymer；Purification process while example 1.Polymer yield
It is 65%.
Embodiment 6 is by the methyl methacrylate of 80 parts by weight, the isobomyl acrylate rouge of 14 parts by weight, 6 parts by weight
Methacrylic acid, 2 × 10-4The initiator DTBP of parts by weight, 4 × 10-4The TDDM of parts by weight and the dimethylbenzene of 30 parts by weight fall
Enter in the heat-resistant tube of 38mL, is configured to mixed solution.Then heat-resistant tube is placed on heating magnetic agitator and is heated.Polymerization
Temperature is 130 DEG C, and polymerization time is 4 hours, obtains the solution of terpolymer；Purification process while example 1.Polymer yield
It is 64%.
Embodiment 7 by the methyl methacrylate of 90 parts by weight, the isobomyl acrylate rouge of 8 parts by weight, 2 parts by weight third
E pioic acid methyl ester, 2 × 10-4The initiator DTBP of parts by weight, 4 × 10-4The TDDM of parts by weight and the toluene of 30 parts by weight pour into
In the heat-resistant tube of 38mL, it is configured to mixed solution.Then heat-resistant tube is placed on heating magnetic agitator and is heated.Polymerization temperature
Degree is 120 DEG C, and polymerization time is 4 hours, obtains the solution of terpolymer；Purification process while example 1.Polymer yield is
63%。
Embodiment 8 is by the methyl methacrylate of 80 parts by weight, the isobomyl acrylate rouge of 16 parts by weight, 4 parts by weight
Methyl acrylate, 2 × 10-4The initiator DTBP of parts by weight, 4 × 10-4The TDDM of parts by weight and the toluene of 30 parts by weight pour into
In the heat-resistant tube of 38mL, it is configured to mixed solution.Then heat-resistant tube is placed on heating magnetic agitator and is heated.Polymerization temperature
Degree is 120 DEG C, and polymerization time is 4 hours, obtains the solution of terpolymer；Purification process while example 1.Polymer yield is
60%。
Embodiment 9 is by the methyl methacrylate of 80 parts by weight, the isobomyl acrylate rouge of 14 parts by weight, 6 parts by weight
Methyl acrylate, 2 × 10-4The initiator DTBP of parts by weight, 4 × 10-4The TDDM of parts by weight and the toluene of 30 parts by weight pour into
In the heat-resistant tube of 38mL, it is configured to mixed solution.Then heat-resistant tube is placed on heating magnetic agitator and is heated.Polymerization temperature
Degree is 120 DEG C, and polymerization time is 4 hours, obtains the solution of terpolymer；Purification process while example 1.Polymer yield is
63%。
Embodiment 10 is by the methyl methacrylate of 90 parts by weight, the isobomyl acrylate rouge of 8 parts by weight, 2 parts by weight
Styrene, 2 × 10-4The initiator DTBP of parts by weight, 4 × 10-4The TDDM of parts by weight and the toluene of 30 parts by weight pour into 38mL's
In heat-resistant tube, it is configured to mixed solution.Then heat-resistant tube is placed on heating magnetic agitator and is heated.Polymerization temperature is
140 DEG C, polymerization time is 4 hours, obtains the solution of terpolymer；Purification process while example 1.Polymer yield is 66%.
Embodiment 11 is by the methyl methacrylate of 70 parts by weight, the isobomyl acrylate rouge of 20 parts by weight, 10 parts by weight
Styrene, 2 × 10-4The initiator DTBP of parts by weight, 4 × 10-4The TDDM of parts by weight and the toluene of 30 parts by weight pour into 38mL
Heat-resistant tube in, be configured to mixed solution.Then heat-resistant tube is placed on heating magnetic agitator and is heated.Polymerization temperature is
140 DEG C, polymerization time is 4 hours, obtains the solution of terpolymer；Purification process while example 1.Obtained polymer yield
It is 68%.
Embodiment 12 is by the methyl methacrylate of 80 parts by weight, the isobomyl acrylate rouge of 14 parts by weight, 6 parts by weight
Styrene, 2 × 10-4The initiator B PO of parts by weight, 4 × 10-4The NOM of parts by weight and the dimethylbenzene of 30 parts by weight pour into 38mL's
In heat-resistant tube, it is configured to mixed solution.Then heat-resistant tube is placed on heating magnetic agitator and is heated.Polymerization temperature is
130 DEG C, polymerization time is 4 hours, obtains the solution of terpolymer；Purification process while example 1.Polymer yield is 64%.
The method that embodiment 13 uses bulk polymerization.
By the methyl methacrylate of 80 parts by weight, the isobomyl acrylate rouge of 14 parts by weight, 6 parts by weight metering system
Amide, 1 × 10-4The initiator DTBP of parts by weight, 2 × 10-4The TDDM of parts by weight is poured into the heat-resistant tube of 38mL, is configured to mix
Close solution.Then heat-resistant tube is placed on heating magnetic agitator and is heated.Polymerization temperature is 130 DEG C, and polymerization time is 4 small
When, obtain the solution of terpolymer；Purification process while example 1.Polymer yield is 62%.
The method that embodiment 14 uses bulk polymerization.
By the methyl methacrylate of 70 parts by weight, the isobomyl acrylate rouge of 20 parts by weight, 10 parts by weight styrene,
2×10-4The initiator DTBP of parts by weight, 4 × 10-4The TDDM of parts by weight is poured into the heat-resistant tube of 38mL, is configured to mix molten
Liquid.Then heat-resistant tube is placed on heating magnetic agitator and is heated.Polymerization temperature is 100 DEG C, and polymerization time is 6 hours,
Obtain the solution of terpolymer；Purification process while example 1.Polymer yield is 60%.
The method that embodiment 15 uses bulk polymerization.
By the methyl methacrylate of 80 parts by weight, the isobomyl acrylate rouge of 14 parts by weight, 6 parts by weight metering system
Acid, 2 × 10-4The initiator DTBP of parts by weight, 4 × 10-4The TDDM of parts by weight is poured into the heat-resistant tube of 38mL, is configured to mix
Solution.Then heat-resistant tube is placed on heating magnetic agitator and is heated.Polymerization temperature is 130 DEG C, and polymerization time is 4 small
When, obtain the solution of terpolymer；Purification process while example 1.Polymer yield is 70%.
The method that embodiment 16 uses bulk polymerization.
By the methyl methacrylate of 90 parts by weight, the isobomyl acrylate rouge of 8 parts by weight, 2 parts by weight acrylic acid first
Ester, 2 × 10-4The initiator DTBP of parts by weight, 4 × 10-4The TDDM of parts by weight is poured into the heat-resistant tube of 38mL, is configured to mix
Solution.Then heat-resistant tube is placed on heating magnetic agitator and is heated.Polymerization temperature is 160 DEG C, and polymerization time is 3.5 small
When, obtain the solution of terpolymer；Purification process while example 1.Polymer yield is 64%.
The polymer that above-described embodiment 1 ~ 16 obtains carries out thermal performance test and molecular weight and its distribution tests, water suction
The test of rate.Specific data are as shown in Table 1 and Table 2.
As can be seen that the method for using polymerisation in solution from table 1 and 2.Obtained polymethylacrylic acid acid methyl terpolymer
Glass transition temperature TgUp to 150.9 DEG C, thermal decomposition temperature T is originateddUp to 300.4 DEG C, while the water absorption rate of copolymer is only
It is 0.33%.
Using the method for bulk polymerization.The glass transition temperature T of obtained polymethylacrylic acid acid methyl terpolymergIt can
Up to 149.6 DEG C, thermal decomposition temperature T is originateddUp to 292.9 DEG C, while the water absorption rate of copolymer is only 0.33%.
Fig. 1 is the DSC curve of polymethyl methacrylate polymers, wherein (a) embodiment 13；(b) embodiment 16；(c) real
Apply example 22；(d) embodiment 19.It can be seen from the figure that embodiment 13,16,19 and 22 be respectively Third monomer be MAAM, MAA,
The copolymer of MA, St, the glass transition temperature T of embodiment 13gReach 149.6 DEG C.
Fig. 2 is the TGA curve of polymethyl methacrylate copolymer, (a) embodiment 19；(b) embodiment 16；(c) real
Apply example 13；(d) embodiment 22.It can be seen from the figure that the thermal stability of embodiment 19,16,13,22 will be got well, and embodiment 13
(i.e. Third monomer is MAAM) its thermal stability is best, originates thermal decomposition temperature TdReach 292.9 DEG C.Fig. 3 is that this is respectively adopted
The DSC curve of body and solution polymerization process synthesis, wherein (a) embodiment 3；(b) embodiment 13.
Fig. 4 is the TGA curve that ontology and solution polymerization process synthesis is respectively adopted, wherein (a) embodiment 3；(b) embodiment
13.It can be seen from the figure that the starting thermal decomposition temperature T of embodiment 3dUp to 300.4 DEG C；The starting of embodiment 13 thermally decomposes temperature
Spend TdIt is 292.9 DEG C；And whole thermal stability is the same, and this demonstrate whether bulk polymerization or polymerisation in solutions, can
Synthesize the copolymer of better heat stability.
Claims (1)
1. a kind of preparation method of methylmethacrylate copolymer, which is characterized in that using the preparation method of polymerisation in solution, step
Rapid and condition is as follows:
(1) according to weight, monomer I: monomer II: monomer III: solvent: initiator: chain-transferring agent is 70 ~ 90 parts: 8 ~ 20
Part: 2 ~ 10 parts: 30 parts: 1 × 10-5~1×10-4Part: 1 × 10-5~4×10-4Part；The monomer I is methyl methacrylate；
The monomer II is selected from isobornyl methacrylate or isobornyl acrylate；The monomer III is selected from styrene, third
E pioic acid methyl ester, methacrylic acid or Methacrylamide；The initiator be selected from azo-bis-iso-dimethyl (AIBME),
Azodiisobutyronitrile (AIBN), benzoyl peroxide (BPO) or di-t-butyl peroxide (DTBP)；The chain-transferring agent is selected from
N-octyl mercaptan (NOM) or tert-dodecylmercaotan (TDDM)；The solvent is selected from toluene or dimethylbenzene；
(2) according to said ratio, by monomer I, monomer II, monomer III, solvent, initiator and chain-transferring agent are added in heat-resistant tube,
Be configured to mixed solution, then, by heat-resistant tube be placed on heating magnetic agitator heat polymerize, polymerization temperature be 100 ~
160 DEG C, polymerization reaction time is 3 ~ 6 hours；
(3) purification process: taking the mixed solution of above-mentioned preparation to pour into chloroform and make it dissolve, and then will pour into together again
It in anhydrous methanol and stirs, obtains white flocculent polymer, filter, washing, then filter, solids is spontaneously dried 12 hours
Afterwards, drying 24 hours in vacuum drying oven are put into, object is obtained.
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| CN106749850A (en) * | 2016-11-28 | 2017-05-31 | 苏州双象光学材料有限公司 | A kind of preparation method of damage resistant, high-impact PMMA materials |
| CN108409973A (en) * | 2017-12-27 | 2018-08-17 | 管燕 | A kind of rubber and preparation method thereof for Foldable basin |
| EP3805312B1 (en) | 2019-10-08 | 2023-12-06 | Trinseo Europe GmbH | Impact modified copolymers of (meth)acrylate esters and/or free radically polymerizable monomers containing nucleophilic groups |
| CN113120880A (en) * | 2019-12-30 | 2021-07-16 | Tcl集团股份有限公司 | Preparation method of polymer carbon dots, polymer carbon dot film, preparation method and application |
| CN113336882B (en) * | 2021-05-24 | 2022-11-04 | 博立尔化工（扬州）有限公司 | Process for preparing PMMA resin with narrow molecular weight distribution by adopting intermittent bulk polymerization method |
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| CN102585085B (en) * | 2011-12-29 | 2014-04-02 | 广州科苑新型材料有限公司 | Polymethacrylate copolymer and photodiffusion section bar prepared by adopting same as raw material |
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