CN103374108B - Three block propylene acid esters process for preparation of thermoplastic elastomer - Google Patents
Three block propylene acid esters process for preparation of thermoplastic elastomer Download PDFInfo
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Abstract
The present invention relates to a kind of three block propylene acid esters process for preparation of thermoplastic elastomer: the linear two ends of first preparing narrow molecular weight distribution are the butyl polyacrylate of halogen group, be macromole evocating agent again with butyl polyacrylate, Methyl Methacrylate monomer polymerization, is gathered (methyl methacrylate-b-butyl acrylate-b-methyl methacrylate).The method can reduce catalyst levels, reduces polymerization process to the susceptibility of oxygen; Utilize environmentally friendly reductive agent; Aftertreatment is simple, reduces industrial cost.
Description
Technical field
The invention belongs to chemical material field, relate to three inlay section thermal plastic elastic bodies of synthesizing methylmethacrylate and butyl acrylate.
Background technology
There is the elasticity of rubber, the class elastomerics that under high temperature, plasticization is shaping under thermoplastic elastomer (TPE) refers to normal temperature.Its product had both possessed the snappiness of traditional cross-linking vulcanized rubber, ageing-resistant, the every excellent properties of oil-proofness, possessed again the wider feature of common plastics processing mode simultaneously.Therefore the various fields such as automobile, building, housed device, electric wire, cable, electronic product, food product pack, medicine equipment are widely used in.
Applying maximum in conventional thermoplastic's elastomerics is styrene analog thermoplastic elastomer, as styrene-isoprene-phenylethene (SIS), and styrene-butadiene-styrene (SBS) and their hydride SEPS, SEBS etc.Wherein SBS is mainly used as material for shoes, and obtains widespread use as the impact modifier of polystyrene and the elastomeric modification agent of pitch, and SIS is then mainly used as tackiness agent.But due to the existence of phenyl ring and unsaturated double-bond in its elastomerics, also make its anti-oxidant, ageing-resistant and transparency be affected.Compared with traditional styrenic elastomer, the research of esters of acrylic acid triblock copolymer thermoplastic elastomer receives increasing concern, this is because Achievement of acrylate type thermo plastic elastomers performance in anti-oxidant, ageing-resistant, transparent and oil-proofness etc. is more excellent.
The method that traditional method adds different monomers by order obtains segmented copolymer, synthesizes the thermoplastic elastomer being made up of, having multiple premium properties polarity and non-polar monomer.And adopt bifunctional initiator to carry out living polymerization, only need add twice monomer can obtain A-B-A type triblock copolymer.The elastomeric requirement of preparation acrylate thermoplastic is that middle soft segment molecule quality is comparatively large, T
glower, the hard segment molecule quality at two ends is less, Tg is higher.Butyl acrylate is selected to be the first monomer, methyl methacrylate is second comonomer, design the molecular mass of each segment, carry out block polymerization, namely obtain poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate) (PMMA-b-PBA-b-PMMA) triblock copolymer that molecular mass increases by design load, its distribution is substantially constant, transformation efficiency is higher.
Hinder the subject matter of aforesaid method industrial applications to be catalyzer needed for it to be the metallic salt (most representative is cuprous halide) of low-oxidation-state, easily oxidized, need refining before using and consumption is very large, in mass polymerization, concentration accounts for monomer mole ratio close to 1%(usually).The use of a large amount of catalyzer not only increases production cost, and removing and recycling of catalyzer is also a masty problem, and industrialization difficulty is comparatively large, not easily carries out.
CN101466751A discloses " preparing the method for the ABA triblock copolymer based on (methyl) acrylate ", and its catalyst levels is about more than 2% of monomer molar amount; CN1989216A discloses " (methyl) acrylate block copolymer pressure sensitive adhesives ", and wherein triblock copolymer end is carbon-bromine key that bond energy is lower, has certain influence for the heat-resisting of the finished product and ageing-resistant performance.
Summary of the invention
The technical problem to be solved in the present invention reduces catalyst levels, reduces polymerization process to the susceptibility of oxygen; Utilize environmentally friendly reductive agent; Aftertreatment is simple, reduces industrial cost.
The present invention first prepares molecular weight between 2000 ~ 90000 and the narrower two ends of molecular weight distribution are that (molecular weight can design as required for the linear butyl polyacrylate of carbon-halogen bond, specific design method is shown in embodiment, molecular weight distribution <2.0), be macromole evocating agent again with butyl polyacrylate, (molecular weight can design Methyl Methacrylate monomer as required, specific design method is shown in embodiment, molecular weight distribution <2.0) polymerization, gathered (methyl methacrylate-b-butyl acrylate-b-methyl methacrylate).
The preparation method of a kind of poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate), carries out according to following step:
(1) Butyl Acrylate Monomer, difunctionality organic halogen initiator, catalyzer, part, reductive agent and solvent are added in reaction vessel, after reaction system being vacuumized, be filled with nitrogen or argon gas, at 65 ~ 90 DEG C, react 6 ~ 25 hours under magnetic agitation;
Initiator wherein described in (1) is difunctionality halogenated organic compound, and as two alpha-brominated isopropylformic acid BDO esters, two alpha-brominated isopropylformic acid glycol esters, synthesize linear butyl polyacrylate; Catalyzer is high-valency metal halide catalyst, as CuBr
2, CuCl
2deng, preferred CuBr2; Part is five methyl diethylentriamine (PMDETA), three-(N, N-dimethyl aminoethyl) amine (Me
6tREN) etc.; Reductive agent is xitix (AA), glucose, stannous octoate (Sn (EH)
2) etc.; Wherein said solvent is ethyl acetate, tetrahydrofuran (THF), toluene, methyl-phenoxide or wherein two kinds and above mixture.
Butyl Acrylate Monomer wherein described in (1): initiator=20:1 ~ 700:1(mol ratio), high-valency metal halide catalyst: Butyl Acrylate Monomer=0.005:100 ~ 0.05:100(mol ratio), high-valency metal halide catalyst: part=1:5 ~ 1:30(mol ratio), high-valency metal halide catalyst: reductive agent=1:5 ~ 1:30(mol ratio), quantity of solvent is 20 ~ 50%(massfraction of whole system).
(2) the product at reduced pressure distillation obtained is removed solvent and is butyl polyacrylate, and its molecular weight ranges is 2000 ~ 90000, molecular weight distribution <2.0; Using the macromole evocating agent of this polymkeric substance as step (3).
(3) above-mentioned butyl polyacrylate, methyl methacrylate monomer, catalyzer, part, reductive agent and solvent are added in reaction vessel, after reaction system being vacuumized, be filled with nitrogen or argon gas, at 60 DEG C ~ 85 DEG C, react 5 ~ 30 hours under magnetic agitation;
Catalyzer wherein described in (3) is high-valency metal halide catalyst, as CuBr
2, CuCl
2deng, preferred CuCl
2; Part is five methyl diethylentriamine (PMDETA), three-(N, N-dimethyl aminoethyl) amine (Me
6tREN) etc.; Reductive agent is xitix (AA), glucose, stannous octoate (Sn (EH)
2) etc.; Wherein said solvent is ethyl acetate, tetrahydrofuran (THF), toluene, methyl-phenoxide or wherein two kinds and above mixture.
Butyl polyacrylate macromole evocating agent wherein described in (3): methyl methacrylate monomer=1:20 ~ 1:800(mol ratio), catalyzer: methyl methacrylate monomer=0.005:100 ~ 0.05:100(mol ratio), catalyzer: part=1:5 ~ 1:20(mol ratio), catalyzer: reductive agent=1:5 ~ 1:30(mol ratio), quantity of solvent be the quality summation of monomer and macromole evocating agent 50 ~ 200%(massfraction).
(4) products therefrom underpressure distillation is removed solvent and be poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate) that segment two ends are carbon-halogen bond, its molecular weight is 3000 ~ 145000, molecular weight distribution <2.0;
(5) can poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate) of gained, (2-hydroxyethyl)methylamine) (MMEA), triethylamine (TEA) and solvent be joined in reaction vessel, nitrogen or argon gas is filled with after reaction system being vacuumized, at 80 DEG C ~ 100 DEG C, react 20 ~ 40 hours under magnetic agitation, reaction terminates triethylamine and methyl monoethanolamine in rear removing system and namely obtains poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate) that segment two ends are hydroxyl.
(2-hydroxyethyl)methylamine) wherein described in (5): triethylamine: poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate)=25:5:1.Solvent is toluene, and add-on is about 30% ~ 50% of poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate).
Tool of the present invention has the following advantages and beneficial effect:
1. first prepare butyl polyacrylate, and the polymerization of second segment methyl methacrylate is caused as macromole evocating agent, synthesis subject copolymers poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate), can ensure that polymericular weight is controlled and structure is clear and definite, and catalyst levels is low, minimum needs 0.005% of amount of monomer, does not need Removal of catalyst, polymerization process declines to the susceptibility of oxygen, and reaction is more easily carried out.
2. design can be needed to prepare first paragraph butyl polyacrylate and the second segment polymethylmethacrylate of different molecular weight according to difference, carry out different application.And poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate) that obtain can carry out terminal hydroxy group process further,-X the halogen group replacing two ends is-OH, improves heat aging property and the chemical reaction ability of poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate).
3. the present invention can use when preparing second segment polymethylmethacrylate and be polymerized (CuBr with first paragraph butyl polyacrylate
2) different Catalysts Cu Cl
2, the molecular weight distribution of polymethylmethacrylate is better controlled by halogen exchange.Accompanying drawing explanation
The GPC result of gained three block M nBM and PBA macromole evocating agent in Fig. 1 embodiment 1 and 2
Embodiment
Below by specific embodiment, the present invention is described in further detail, but the embodiment of the present invention is not limited to this.
Embodiment 1:
(1) preparation of difunctionality macromole evocating agent butyl polyacrylate: preset molecular weight 60000 (initiator: monomer=1:600,
Transformation efficiency 80% stopped reaction)
Adding 76.90g(0.6mol successively with in the 250mL four-hole boiling flask of thermometer) monomers B A, 0.3880g(1 × 10
-3mol) bifunctional initiator two alpha-brominated isopropylformic acid BDO ester, 0.02680g(1.2 × 10
-4mol) Catalysts Cu Br
2, 0.3122g(1.8 × 10
-3mol) part PMDETA, 0.9720g(2.4 × 10
-3mol) reductive agent Sn (EH) 2,15.23g toluene, 5g methyl-phenoxide, mixes, then vacuum nitrogen filling gas, heats up and stirs, and reacts at 75 DEG C.Every 30min sampling, survey molecular weight and molecular weight distribution with gas-chromatography survey monomer conversion and gel permeation chromatography.After reaction 12h, transformation efficiency reaches 79.5%, and reaction terminates.Solvent in underpressure distillation removal system, obtains pale yellow transparent viscous product.Product quality is 52.9446g, and productive rate is 86.60%.GPC test is carried out to product, obtains the Mn=54400 of PBA macromole evocating agent, molecular weight distribution PDI=1.24.
(2) preparation of triblock copolymer poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate): preset
Molecular weight 100000 (initiator: monomer=1:500, transformation efficiency 90% stopped reaction)
Adding 10.01g(0.1mol successively with in the 100mL four-hole boiling flask of thermometer) monomers methyl methacrylate (MMA), 10.88g(2 × 10
-4mol) butyl polyacrylate (PBA) macromole evocating agent, 0.004467g(2 × 10
-5mol) Catalysts Cu Br
2, 0.5204g(3 × 10
-4mol) part PMDETA, 0.1620g(4 × 10
-4mol) reductive agent Sn (EH)-
2, 7.19g toluene, 3.05g methyl-phenoxide, mixes, then vacuum nitrogen filling gas, heat up stir, at 75 DEG C react.Every 30min sampling, survey molecular weight and molecular weight distribution with gas-chromatography survey monomer conversion and gel permeation chromatography.After reaction 14.75h, transformation efficiency reaches 87.5%, and reaction terminates.Solvent in underpressure distillation removal system, obtains pale yellow transparent solid product.Product quality is 16.83g, and productive rate is 92.13%.GPC test is carried out to product, obtains the Mn=101300 of PMMA-b-PBA-b-PMMA triblock copolymer, molecular weight distribution PDI=1.47.
(3) preparation of terminal hydroxy group poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate)
(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate) (1.481 × 10 is being gathered with adding 15.02g in the 100mL four-hole boiling flask of thermometer successively
-4mol), 0.2781gN-methyl monoethanolamine (MMEA) (0.003702mol), 0.07493g triethylamine (TEA) (0.0007405mol), argon gas is filled with after reaction system being vacuumized, at 100 DEG C, react 20 hours under magnetic agitation, after reaction terminates, triethylamine is removed through underpressure distillation, dry the excessive (2-hydroxyethyl)methylamine) of removing through precipitation again, obtain poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate) 8.25g of the membranaceous product end hydroxyl of pale yellow transparent.
Embodiment 2:
(1) the difunctionality macromole evocating agent identical with embodiment 1 is used.
(2) preparation of triblock copolymer poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate): preset
Molecular weight 100000 (initiator: monomer=1:500, transformation efficiency 90% stopped reaction)
Adding 10.07g(0.1mol successively with in the 100mL four-hole boiling flask of thermometer) monomers methyl methacrylate (MMA), 10.65g(2 × 10
-4mol) butyl polyacrylate (PBA) macromole evocating agent, 0.002690g(2 × 10
-5mol) Catalysts Cu Cl
2, 0.3469g(3 × 10
-5mol) part PMDETA, 0.0081g(2 × 10
-5mol) reductive agent Sn (EH)-2,15.57g toluene, 5.13g methyl-phenoxide, mixes, then vacuum nitrogen filling gas, heats up and stirs, and reacts at 75 DEG C.Every 30min sampling, survey molecular weight and molecular weight distribution with gas-chromatography survey monomer conversion and gel permeation chromatography.After reaction 8.5h, transformation efficiency reaches 76.5%, and reaction terminates.Solvent in underpressure distillation removal system, obtains pale yellow transparent solid product.Product quality is 15.81g, and productive rate is 86.55%.GPC test is carried out to product, obtains the Mn=95200 of PMMA-b-PBA-b-PMMA triblock copolymer, molecular weight distribution PDI=1.27.
(3) preparation of terminal hydroxy group poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate)
(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate) (1.481 × 10 is being gathered with adding 14.96g in the 100mL four-hole boiling flask of thermometer successively
-4mol), 0.2850gN-methyl monoethanolamine (MMEA) (0.003702mol), 0.07515g triethylamine (TEA) (0.0007405mol), nitrogen is filled with after reaction system being vacuumized, at 80 DEG C, react 40 hours under magnetic agitation, after reaction terminates, triethylamine is removed through underpressure distillation, dry the excessive (2-hydroxyethyl)methylamine) of removing through precipitation again, obtain poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate) 7.75g of the membranaceous product end hydroxyl of pale yellow transparent.
Embodiment 3:
(1) preparation of difunctionality macromole evocating agent butyl polyacrylate: preset molecular weight 2000 (initiator: monomer=1:20, transformation efficiency 80% stopped reaction)
Adding 76.78g(0.6mol successively with in the 250mL four-hole boiling flask of thermometer) monomers B A, 10.8g(0.03mol) the alpha-brominated isopropylformic acid Isosorbide-5-Nitrae-glycol ester of bifunctional initiator, 0.04048g(3 × 10
-4mol) Catalysts Cu Cl2,0.7005g(1.5 × 10
-3mol) part three-(N, N-dimethyl aminoethyl) amine (Me
6tREN), 0.2645g(1.5 × 10
-3mol) xitix (AA), 15.15gs tetrahydrofuran (THF), 3.20g toluene, mixes, and then vacuumizes applying argon gas, heats up and stirs, and reacts at 60 DEG C.Every 30min sampling, survey molecular weight and molecular weight distribution with gas-chromatography survey monomer conversion and gel permeation chromatography.After reaction 6.5h, transformation efficiency reaches 85.2%, and reaction terminates.Solvent in underpressure distillation removal system, obtains pale yellow transparent viscous product.Product quality is 45.30g, and productive rate is 78.5%.GPC test is carried out to product, obtains the Mn=2250 of PBA macromole evocating agent, molecular weight distribution PDI=1.17.
(2) preparation of triblock copolymer poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate): preset molecular weight 3500 (initiator: monomer=1:20, transformation efficiency 75% stopped reaction)
Adding 10.16g(0.1mol successively with in the 100mL four-hole boiling flask of thermometer) monomers methyl methacrylate (MMA), 11.25g(5 × 10
-3mol) butyl polyacrylate (PBA) macromole evocating agent, 0.006795g(5 × 10
-5mol) Catalysts Cu Cl
2, 0.0580g(2.5 × 10
-4mol) part three-(N, N-dimethyl aminoethyl) amine (Me
6tREN), 0.6095g(1.5 × 10
-3mol) reductive agent Sn (EH)
2, 17.01g ethyl acetate, 15.13g toluene, mixes, and then vacuumizes applying argon gas, heat up stir, at 85 DEG C react.Every 30min sampling, survey molecular weight and molecular weight distribution with gas-chromatography survey monomer conversion and gel permeation chromatography.After reaction 4.5h, transformation efficiency reaches 73.5%, and reaction terminates.Solvent in underpressure distillation removal system, obtains pale yellow transparent solid product.Product quality is 14.08g, and productive rate is 80.5%.GPC test is carried out to product, obtains the Mn=3870 of PMMA-b-PBA-b-PMMA triblock copolymer, molecular weight distribution PDI=1.24.
Embodiment 4:
(1) preparation of difunctionality macromole evocating agent butyl polyacrylate: preset molecular weight 80000 (initiator: monomer=1:700, transformation efficiency 85% stopped reaction)
Adding 76.92g(0.6mol successively with in the 250mL four-hole boiling flask of thermometer) monomers B A, 0.3327g(8.57 × 10
-4mol) bifunctional initiator alpha-brominated isopropylformic acid BDO ester, 0.006710g(3 × 10
-5mol) Catalysts Cu Br
2, 0.1565g(9 × 10
-4mol) part PMDETA, 0.1592g(9 × 10
-4mol) reductive agent xitix (AA), 35.25g toluene, 3.89g methyl-phenoxide, mixes, and then vacuumizes applying argon gas, heats up and stirs, and reacts at 85 DEG C.Every 30min sampling, survey molecular weight and molecular weight distribution with gas-chromatography survey monomer conversion and gel permeation chromatography.After reaction 5h, transformation efficiency reaches 87.6%, and reaction terminates.Solvent in underpressure distillation removal system, obtains pale yellow transparent viscous product.Product quality is 54.24g, and productive rate is 80.50%.GPC test is carried out to product, obtains the Mn=84800 of PBA macromole evocating agent, molecular weight distribution PDI=1.40.
(2) preparation of triblock copolymer poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate): preset molecular weight 150000 (initiator: monomer=1:800, transformation efficiency 80% stopped reaction)
Adding 10.18g(0.1mol successively with in the 100mL four-hole boiling flask of thermometer) monomers methyl methacrylate (MMA), 10.72g(1.25 × 10
-4mol) butyl polyacrylate (PBA) macromole evocating agent, 0.01130g(5 × 10
-5mol) Catalysts Cu Br
2, 0.2617g(1.5 × 10
-3mol) part PMDETA, 0.04405g(2.5 × 10
-4mol) reductive agent xitix (AA), 40.22g methyl-phenoxide, mix, then vacuum nitrogen filling gas, heats up and stir, and reacts at 60 DEG C.Every 30min sampling, survey molecular weight and molecular weight distribution with gas-chromatography survey monomer conversion and gel permeation chromatography.After reaction 23h, transformation efficiency reaches 78.8%, and reaction terminates.Solvent in underpressure distillation removal system, obtains pale yellow transparent solid product.Product quality is 13.73g, and productive rate is 73.26%.GPC test is carried out to product, obtains the Mn=157500 of PMMA-b-PBA-b-PMMA triblock copolymer, molecular weight distribution PDI=1.31.
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.Those skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein are applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art are according to announcement of the present invention, and the amendment made for the present invention all should within protection scope of the present invention.
Claims (4)
1. the preparation method of poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate), carries out according to following step:
(1) Butyl Acrylate Monomer, difunctionality organic halogen initiator, catalyzer, part, reductive agent and solvent are added in reaction vessel, nitrogen or argon gas is filled with after reaction system being vacuumized, at 65 ~ 90 DEG C, react 6 ~ 25 hours under magnetic agitation;
Initiator wherein described in (1) is difunctionality halogenated organic compound, and be selected from two alpha-brominated isopropylformic acid BDO esters, two alpha-brominated isopropylformic acid glycol esters, synthesize linear butyl polyacrylate; Catalyzer is high-valency metal halide catalyst, is selected from CuBr
2, CuCl
2; Part is five methyl diethylentriamine (PMDETA), three-(N, N-dimethyl aminoethyl) amine (Me
6tREN); Reductive agent is xitix (AA), glucose, stannous octoate (Sn (EH)
2); Wherein said solvent is ethyl acetate, tetrahydrofuran (THF), toluene, methyl-phenoxide or wherein two kinds and above mixture;
(2) the product at reduced pressure distillation that step (1) obtains is removed solvent and is butyl polyacrylate; Using the macromole evocating agent of this polymkeric substance as step (3);
(3) above-mentioned butyl polyacrylate, methyl methacrylate monomer, catalyzer, part, reductive agent and solvent are added in reaction vessel, nitrogen or argon gas is filled with after reaction system being vacuumized, at 60 DEG C ~ 85 DEG C, react 5 ~ 30 hours under magnetic agitation;
Catalyzer wherein described in (3) is CuBr
2or CuCl
2; Part is five methyl diethylentriamine, three-(N, N-dimethyl aminoethyl) amine; Reductive agent is xitix, glucose, stannous octoate; Wherein said solvent is ethyl acetate, tetrahydrofuran (THF), toluene, methyl-phenoxide or wherein two kinds and above mixture;
(4) products therefrom underpressure distillation is removed solvent and be poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate) that segment two ends are carbon-halogen bond;
(5) poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate) of gained, (2-hydroxyethyl)methylamine), triethylamine and solvent are joined in reaction vessel, nitrogen or argon gas is filled with after reaction system being vacuumized, at 80 DEG C ~ 100 DEG C, react 20 ~ 40 hours under magnetic agitation, reaction terminates triethylamine and methyl monoethanolamine in rear removing system and namely obtains poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate) that segment two ends are hydroxyl.
2. the preparation method of one according to claim 1 poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate), Butyl Acrylate Monomer wherein described in (1) and initiator mol ratio are 20:1 ~ 700:1, high-valency metal halide catalyst and Butyl Acrylate Monomer mol ratio are 0.005:100 ~ 0.05:100, high-valency metal halide catalyst and part mol ratio are 1:5 ~ 1:30, high-valency metal halide catalyst and reductive agent mol ratio are 1:5 ~ 1:30, and solvent quality is 20 ~ 50% of whole system quality.
3. the preparation method of one according to claim 1 poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate), butyl polyacrylate macromole evocating agent wherein described in (3) and methyl methacrylate monomer mol ratio are 1:20 ~ 1:800, catalyzer and methyl methacrylate monomer mol ratio are 0.005:100 ~ 0.05:100, catalyzer and part mol ratio are 1:5 ~ 1:20, catalyzer and reductive agent mol ratio are 1:5 ~ 1:30, and solvent quality is 50 ~ 200% of the quality summation of monomer and macromole evocating agent.
4. the preparation method of one according to claim 1 poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate), the (2-hydroxyethyl)methylamine) wherein described in (5): triethylamine: poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate)=25:5:1; Solvent is toluene, and add-on is 30% ~ 50% of poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate).
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| CN104072921A (en) * | 2014-07-01 | 2014-10-01 | 常州大学 | Toughened polymethyl methacrylate mixture and preparation method thereof |
| RU2017140844A (en) * | 2015-04-27 | 2019-05-27 | Те Риджентс Оф Те Юниверсити Оф Мичиган | LONG-TERM ANTI-EDUCATION SURFACE |
| CN106833099B (en) * | 2017-02-17 | 2020-07-07 | 重庆文理学院 | Surface control agent and preparation method thereof |
| CN107486043A (en) * | 2017-09-14 | 2017-12-19 | 天津工业大学 | A kind of preparation method of amphipathic three block copolymer modified polyvinilidene fluoride film |
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| CN1173504A (en) * | 1996-08-12 | 1998-02-18 | 埃勒夫阿托化学有限公司 | Process for controlled radical polymerization or copolymerization of (meth) acrylic and vinyl monomers, and (CO) polymers obtained |
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