CN112707993A - Styrene- (methyl) acrylate copolymer, preparation method and application - Google Patents
Styrene- (methyl) acrylate copolymer, preparation method and application Download PDFInfo
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Abstract
The invention belongs to the field of polymers, and relates to a styrene- (methyl) acrylate copolymer, and a preparation method and application thereof. The copolymer contains a structural unit A derived from a styrene monomer and a structural unit B derived from a (meth) acrylate monomer; wherein, the content of the structural unit A is 10 to 95 weight percent based on the total weight of the copolymer; the content of the structural unit B is 5-90 wt%; and the total content of the structural unit A and the structural unit B is more than 90 wt%; the weight average molecular weight of the copolymer is more than 20 ten thousand; the copolymer has a ratio of absolute molecular weight to GPC weight average molecular weight Mw.Mall/Mw.GPC of 1.1-2.5. The styrene- (methyl) acrylate copolymer has the performance characteristics of PS and PMMA, and the molecular chain of the styrene- (methyl) acrylate copolymer has a long-chain branched structure, so that the processability of the material in a molten state can be obviously improved.
Description
Technical Field
The invention belongs to the field of polymers, and relates to a styrene- (methyl) acrylate copolymer, a preparation method of the styrene- (methyl) acrylate copolymer, the styrene- (methyl) acrylate copolymer prepared by the method, and application of the styrene- (methyl) acrylate copolymer.
Background
Polystyrene (PS) is transparent, has good rigidity and low hygroscopicity, but has poor toughness and poor weather resistance. Polymethyl methacrylate (PMMA) has high light transmittance and good toughness, but has high hygroscopicity, and the finished product is easy to deform. Therefore, more and more technical methods use styrene and methyl methacrylate as main raw materials to polymerize to obtain styrene-methyl methacrylate copolymer (MS), and the MS integrates various advantages of polystyrene and polymethyl methacrylate, not only has good processing fluidity and low hygroscopicity of polystyrene, but also has weather resistance and excellent optical performance of methyl methacrylate, and can be widely applied to the aspects of daylighting panels, optical lenses, lamps and the like.
Japanese patent laid-open publication No. 2003-075648 discloses a light guide plate having a styrene- (meth) acrylic polymer resin with a weight average molecular weight (Mw) of 6 to 17 ten thousand and a residual content of 3000ppm or less. CN1106026A discloses a solution polymerization method using methanol as a solvent, wherein the monomer conversion rate is 40-75%, and the weight average molecular weight (Mw) is 10-15 ten thousand.
It can be seen that in the prior art, the molecular weight of the MS polymer is not high, the weight average molecular weight Mw is between 6 and 20 ten thousand, the molecules are mainly linear structures, the melt strength is low, and the performance requirements are difficult to meet in the processing processes of plastic uptake, blow molding, film drawing and the like. Therefore, improvement in melt processability of the material is urgently required.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a styrene- (methyl) acrylate copolymer with high melt strength, a preparation method and application thereof.
A first aspect of the present invention provides a styrene- (meth) acrylate copolymer comprising structural units a derived from a styrenic monomer and structural units B derived from a (meth) acrylate-based monomer; wherein, the content of the structural unit A is 10 wt% -95 wt%, preferably 30 wt% -90 wt%, and more preferably 50 wt% -80 wt% based on the total weight of the copolymer; the content of the structural unit B is 5 wt% -90 wt%, preferably 10 wt% -70 wt%, and more preferably 20 wt% -50 wt%; and the total content of the structural unit A and the structural unit B is more than 90 wt%;
the weight average molecular weight of the copolymer is 20 ten thousand or more, preferably 25 ten thousand or more; the copolymer has a ratio of absolute molecular weight to GPC weight average molecular weight Mw.Mall/Mw.GPC ranging from 1.1 to 2.5, preferably from 1.2 to 1.5.
A second aspect of the present invention provides a method for preparing a styrene- (meth) acrylate copolymer, the method comprising: polymerizing a styrene monomer and a (methyl) acrylate monomer under an initiator system to obtain the styrene- (methyl) acrylate copolymer; based on the total weight of the monomers, the amount of the styrene monomers is 10 wt% to 95 wt%, preferably 30 wt% to 90 wt%, and more preferably 50 wt% to 80 wt%, and the amount of the (meth) acrylate monomers is 5 wt% to 90 wt%, preferably 10 wt% to 70 wt%, and more preferably 20 wt% to 50 wt%; and the total amount of the styrene monomer and the (methyl) acrylate monomer is more than 90 wt%;
the initiator system contains a multifunctional initiator, the multifunctional initiator has more than three functional groups capable of forming free radicals, and the content of the multifunctional initiator is more than 50 wt% based on the total weight of the initiator system.
The third aspect of the present invention provides a styrene- (meth) acrylate copolymer obtained by the above-mentioned production method.
The fourth aspect of the present invention provides the use of the above-mentioned styrene- (meth) acrylate copolymer as an optical material.
The styrene- (methyl) acrylate copolymer has the performance characteristics of PS and PMMA, such as high light transmittance and low hygroscopicity, the molecular weight can reach more than 25 ten thousand due to the adoption of the polyfunctional initiator, and the molecular chain has a long branched chain structure, so that the entanglement capacity between the molecular chains can be improved, the processing performance of the material in a molten state is obviously improved, and the more rigorous processing technologies such as plastic uptake, blow molding, film drawing and the like can be met.
In addition, the preparation process is simple and easy to operate. The multistage reactor can ensure stable production of the device, high single-pass conversion rate and effectively reduced operation cost.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
Exemplary embodiments of the present invention will be described in more detail by referring to the accompanying drawings.
FIG. 1 is a schematic diagram of a process for preparing a copolymer having high melt strength according to the present invention.
Description of the reference numerals
X101-first static mixer; r101-first reactor; r102-second reactor; r103-third reactor; r104-fourth reactor; P101/P102/P103/P104-polymerization liquid transfer pump; E201-Heater before flash vaporization; v101-first flash tank; v102-second flash tank.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
A first aspect of the present invention provides a styrene- (meth) acrylate copolymer comprising a structural unit a derived from a styrenic monomer and a structural unit B derived from a (meth) acrylate-based monomer; wherein, the content of the structural unit A is 10 wt% -95 wt%, preferably 30 wt% -90 wt%, and more preferably 50 wt% -80 wt% based on the total weight of the copolymer; the content of the structural unit B is 5 wt% -90 wt%, preferably 10 wt% -70 wt%, and more preferably 20 wt% -50 wt%; and the total content of the structural unit A and the structural unit B is more than 90 wt%;
the weight average molecular weight of the copolymer is 20 ten thousand or more, preferably 25 ten thousand or more; the copolymer has a ratio of absolute molecular weight to GPC weight average molecular weight Mw.Mall/Mw.GPC ranging from 1.1 to 2.5, preferably from 1.2 to 1.5.
According to the present invention, the melt strength of the styrene- (meth) acrylate copolymer may be up to 0.2 to 0.5N, preferably 0.24 to 0.4N.
It is well known to those skilled in the art that GPC-MALL data is used to characterize the degree of polymer branching, i.e., a greater ratio of absolute molecular weight to GPC weight average molecular weight, mw.mall/mw.gpc, indicates a higher degree of polymer branching.
According to the present invention, the styrenic monomer may be selected from one or more of styrene, α -methylstyrene, vinyltoluene, vinylxylene, vinylethylbenzene, isobutylene styrene, t-butylstyrene, bromostyrene, dibromostyrene, chlorostyrene and dichlorostyrene, preferably styrene.
According to the present invention, the (meth) acrylate-based monomer may be one or more selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octadecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, and is preferably methyl methacrylate.
A second aspect of the present invention provides a method for preparing a styrene- (meth) acrylate copolymer, the method comprising: polymerizing a styrene monomer and a (methyl) acrylate monomer under an initiator system to obtain the styrene- (methyl) acrylate copolymer; based on the total weight of the monomers, the amount of the styrene monomers is 10 wt% to 95 wt%, preferably 30 wt% to 90 wt%, and more preferably 50 wt% to 80 wt%, and the amount of the (meth) acrylate monomers is 5 wt% to 90 wt%, preferably 10 wt% to 70 wt%, and more preferably 20 wt% to 50 wt%; and the total amount of the styrene monomer and the (methyl) acrylate monomer is more than 90 wt%;
the initiator system contains a multifunctional initiator, the multifunctional initiator has more than three functional groups capable of forming free radicals, and the content of the multifunctional initiator is more than 50 wt% based on the total weight of the initiator system.
The long chain branching of the copolymers of the invention is achieved by the introduction of a multifunctional initiator. The multifunctional initiator has more than three functional groups, so that the molecular chain grows in multiple directions by taking the multifunctional initiator group as the center to generate a multi-arm molecular chain structure, and a long-chain branch type polymer is formed in the coupling termination of free radicals at the tail end of the molecular chain.
Generally, initiators used for the polymerization of styrenic monomers include monofunctional initiators, difunctional initiators, trifunctional initiators, and tetrafunctional initiators. Trifunctional initiators or tetrafunctional initiators are contemplated for the present invention. Further, the multifunctional initiator is a trifunctional peroxide initiator and/or a tetrafunctional peroxide initiator, particularly a tetrafunctional peroxide initiator, and the optimal branching effect can be obtained.
According to a preferred embodiment of the present invention, the multifunctional initiator is a tetrafunctional peroxide having a structure represented by formula I or formula II;
wherein R is a multifunctional nucleus, such as cyclohexyl or dicyclohexyl propyl, R1、R2、R3Each independently is substituted or unsubstituted C1～C5An alkyl group.
The present invention may employ various tetrafunctional peroxide initiators conventional in the art, either self-made or commercially available. Specifically, the initiator is at least one of 2, 2-bis (4, 4-di (t-butylperoxy) cyclohexyl) propane, [6, 6-bis (5-a-bromoisobutyroyloxy-2-oxopentane) -4, 8-dioxaundecanediol 1,11] bis (a-bromoisobutyrate) and tetrabutyl peroxydicarbonate. The tetrabutyl peroxydicarbonate is, for example, commercially available JWEB 50.
The invention can also select the monofunctional peroxide and the difunctional peroxide to be compounded with the polyfunctional peroxide, and the amount of the initiator for compounding is required to be less than 50 wt% of the total amount of the initiator. The monofunctional peroxide and the difunctional peroxide can be selected from one or more of benzoyl peroxide, lauroyl peroxide, cyclohexanone peroxide, dicyclohexyl peroxydicarbonate, diisopropyl peroxydicarbonate, tert-butyl peroxypivalate, tert-butyl peroxybenzoate, 2-di (tert-butylperoxy) butane, methyl ethyl ketone peroxide, dicumyl peroxide, di-tert-butyl peroxide, and 2, 5-bis (2-ethylhexanoylperoxy) -2, 5-dimethylhexane.
In the present invention, the amount of the multifunctional initiator can be selected conventionally in the art, and is usually 100-2000ppm, preferably 400-1500ppm, and more preferably 600-1200ppm based on the weight of the styrene monomer.
Besides the two comonomers, the copolymer resin can also be added with another monomer or a plurality of monomers to participate in copolymerization. Specifically, for example, (meth) acrylonitrile, (meth) acrylic acid, glycine (meth) acrylate, aminopropyl (meth) acrylate, acrylamide, N-methacrylamide, and the like. The proportion of the other copolymerizable monomer in the copolymer-forming component is 10% by weight or less.
The copolymerization process of the present invention may optionally further comprise an aromatic organic solvent for adjusting the reaction rate and the molecular weight of the final polymer, which is still a bulk polymerization process. The aromatic organic solvent is preferably at least one of benzene, toluene, xylene, and ethylbenzene. The dosage of the aromatic hydrocarbon organic solvent is generally 5-12 wt% of the total amount of the system.
In addition, other additives known in the art, such as antioxidants, melt index modifiers, chain transfer agents, and the like, may also be used in the copolymerization process described above. Specifically, antioxidants include, but are not limited to: 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer (RD); pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (1010); tris (2, 4-di-tert-butylphenyl) phosphite (168); dioctadecyl pentaerythritol diphosphite (618); N-cyclohexyl-N' -phenyl-p-phenylenediamine (4010); 2,2' -methylenebis (4-methyl-6-tert-butylphenol) (2246); n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (1076). Melt index modifiers include, but are not limited to: mineral oil, Polyisobutylene (PIB), silicone oil. Chain transfer agents include, but are not limited to: tert-dodecyl mercaptan, n-dodecyl mercaptan.
The polyesters of the present invention may be prepared by bulk polymerization or solution polymerization, preferably, by a continuous bulk polymerization process. The continuous bulk polymerization is carried out in reactors connected in series in multiple stages, and the copolymer is obtained by devolatilizing (removing unreacted monomers and possible solvents) and granulating the resulting polymerization solution. The continuous bulk preparation process has the characteristics of simple flow, easy operation, low energy consumption and high production efficiency.
The multistage series reactor can be freely combined by selecting a full mixing type reactor (CSTR) and a plug flow type reactor (PFR). Generally, a full mixed reactor (CSTR) is selected to remove the reaction heat by gasifying the monomers, and a Plug Flow Reactor (PFR) is selected to obtain a high-viscosity solution for later polymerization. The invention preferably adopts 1-3 fully mixed reactors (CSTR) and 1-4 Plug Flow Reactors (PFR) to be connected in series, and more preferably adopts 1-2 fully mixed reactors (CSTR) and 2-3 Plug Flow Reactors (PFR) to be connected in series.
In the continuous bulk polymerization of the invention, a prepolymerization stage and a polymerization stage are sequentially carried out, at least one stage of reactor carries out prepolymerization, and the rest reactors carry out polymerization; among them, the polymerization conversion rate in each reactor stage is preferably controlled so that the polymerization conversion rate at the end of the preliminary polymerization stage is 30 to 40%.
According to a preferred embodiment of the present invention, as shown in fig. 1, the multi-stage series reactor comprises a four-stage reactor comprising a one-stage CSTR fully mixed reactor and a three-stage plug flow reactor connected in series in sequence. Wherein, the following operation conditions are preferably adopted in each stage of reactor:
the reaction temperature of the first-stage reactor is controlled to be 90-130 ℃, and preferably 100-120 ℃; the reaction pressure is controlled to be 0.01 to 5.0MPaA, preferably 0.05 to 2 MPaA. A styrene monomer, a methyl (meth) acrylate monomer and a polyfunctional initiator are added thereto to carry out radical polymerization. And when the polymerization conversion rate reaches 8-30%, preferably 15-25%, feeding the materials in the reactor into a second-stage reactor.
The reaction temperature of the second-stage reactor is controlled to be 100-150 ℃, and preferably controlled to be 120-140 ℃; the reaction pressure is controlled to be 0.1 to 10MPaA, preferably 0.5 to 3 MPaA. The polymerization temperature can be controlled in a subarea mode, and the reaction temperature is gradually increased. The second reactor may be fed with a makeup of the methyl (meth) acrylate-based monomer. And when the polymerization conversion rate reaches 25-50%, preferably 30-40%, feeding the materials in the reactor into a third-stage reactor.
The reaction temperature of the third-stage reactor is controlled to be 110-180 ℃, and preferably 130-160 ℃; the reaction pressure is controlled to be 0.1 to 10MPaA, preferably 0.5 to 3 MPaA. The polymerization temperature can be controlled in a subarea mode, and the reaction temperature is gradually increased. And when the polymerization conversion rate reaches 50-70%, feeding the materials in the reactor into a fourth-stage reactor.
The reaction temperature of the fourth-stage reactor is controlled to be 120-200 ℃, and preferably 140-170 ℃; the reaction pressure is controlled to be 0.1 to 10MPaA, preferably 0.5 to 3 MPaA. The polymerization temperature can be controlled in a subarea mode, and the reaction temperature is gradually increased. The final polymerization conversion rate is 80% or more, preferably 85% or more.
The present invention has no specific requirement on the devolatilization mode, and generally, the two-stage flash evaporation is selected to better remove the unreacted monomers and the solvent. In the invention, a two-stage falling strip flash tank is preferably selected, as shown in figure 1, unreacted monomers and a solvent are removed under vacuum, and the devolatilization temperature can be 200-250 ℃. The selection of the devolatilization mode and the process conditions are not intended to limit the present invention.
The invention also provides the styrene- (methyl) acrylate copolymer prepared by the preparation method.
The present invention is further illustrated by the following examples. These examples are provided only for illustrating and explaining the present invention and are not intended to limit the present invention.
In the following examples and comparative examples, the polymer-related data were obtained according to the following test methods:
the unnotched impact strength of the simply supported beam is tested according to GB/T1043-;
flexural strength/flexural modulus were tested in GB/T1040-;
the light transmittance is tested according to GB/T2410-;
the water absorption is tested according to GB/T1034-2008;
and (3) testing molecular weight: determining the relative number average and weight average molecular weight of the polymer by using Agilent high temperature gel permeation chromatograph (PL-GPC 220); the absolute molecular weight of the polymer was determined using a WyattTRI STAR Mini DAWN multiangular laser light scattering instrument (MALLS).
And (3) testing the melt strength: the melt strength tester of Rheotens 97 model of German GOTTFERT company is adopted, the diameter of a die orifice is 2mm, the gap of a drawing wheel is 0.4mm, the distance between the die orifice and the center of the drawing wheel is 60mm, and the drawing acceleration is 20mm/s2The test temperature was 210 ℃.
The following examples all adopt the process flow as shown in fig. 1, and the multistage series reactors include four-stage reactors connected in series in sequence, wherein the first stage reactor R101 is a fully mixed reactor, and the second stage reactor R102, the third stage reactor R103, and the fourth stage reactor R104 are plug flow reactors. An initiator and an optional solvent are mixed in a first static mixer X101, the first static mixer X101 and each polymerization monomer feeding pipeline are connected with an inlet of a first reactor R101, a polymerization liquid delivery pump P101 is arranged on a communicating pipeline between the first stage reactor R101 and a second stage reactor R102, a polymerization liquid delivery pump P102 is arranged on a communicating pipeline between the second stage reactor R102 and a third stage reactor R103, a polymerization liquid delivery pump P103 is arranged on a communicating pipeline between the third stage reactor R103 and a fourth stage reactor R104, the fourth stage reactor R104 is communicated with a flash evaporation front heater E201, the polymerization liquid delivery pump P104 is arranged on the communicating pipeline, the flash evaporation front heater E201 is sequentially connected with a first flash evaporation tank V201 and a second flash evaporation tank V202, solvent recovery is carried out on tank top material flow, and tank bottom material flow enters a granulator.
Example 1
The mass ratio of the styrene monomer to the methyl methacrylate monomer is 7:3, the dosage of the solvent ethylbenzene accounts for 8 wt% of the total amount of the reaction system, and the initiator selects tetrafunctional group peroxide 2, 2-bis (4, 4-di (tert-butylperoxy) cyclohexyl) propane, and the dosage is 800ppm (relative to the styrene monomer). The first reactor (CSTR) was pumped into the second reactor (PFR) at a polymerization temperature of 106 ℃ and a pressure of 0.05MPaA, with a monomer conversion of 21%. The polymerization temperature of the second reactor is 120-135 ℃, the pressure is 2.1MPaA, and when the monomer conversion rate is 46%, the reaction mixture is pumped into a third reactor (PFR). The polymerization temperature of the third reactor is 135-154 ℃, the pressure is 1.5MPaA, and when the monomer conversion rate is 71%, the reaction mixture is pumped into a fourth reactor (PFR) by a pump; the polymerization temperature of the fourth polymerization reactor is 154-170 ℃, the pressure is 0.7MPaA, the monomer conversion rate is 84%, the copolymerization resin is obtained by removing the monomer and the solvent, and the characterization result is shown in Table 1.
Comparative example 1
The monofunctional initiator di-tert-butyl peroxide was used to initiate the free radical polymerization, the other conditions were the same as in example 1, and the characterization results of the obtained polymer are shown in Table 1.
Comparative example 2
The polymerized monomer was styrene only, the other conditions were the same as in example 1, and the characterization results of the obtained polymer are shown in Table 1.
Comparative example 3
The free radical polymerization was initiated by using the difunctional initiator 2.5-dimethyl-2.5-bis (t-butylperoxy) hexane, and the other conditions were the same as in example 1, and the characterization results of the obtained polymer are shown in Table 1.
Example 2
The mass ratio of the styrene monomer to the methyl methacrylate monomer was 5:5, and other conditions were the same as in example 1, and the characterization results of the obtained polymer are shown in Table 1.
Example 3
The mass ratio of styrene monomer to methyl methacrylate monomer was 9:1, and other conditions were the same as in example 1, and the characterization results of the obtained polymer are shown in Table 1.
Example 4
The initiator tetrafunctional peroxide 2, 2-bis (4, 4-di (t-butylperoxy) cyclohexyl) propane was used in an amount of 400 ppm. Other conditions were the same as in example 1, and the characterization results of the obtained polymer are shown in Table 1.
Example 5
According to the process flow shown in the figure 1, the mass ratio of styrene monomer to methyl methacrylate monomer is 7:3, the solvent ethylbenzene accounts for 8 wt% of the total reaction system, and the initiator is selected from tetrafunctional group peroxide [6, 6-bis (5-a-bromoisobutyryloxy-2-oxopentane) -4, 8-dioxyundecanediol 1,11] bis (a-bromoisobutyrate) and is used in an amount of 800ppm (relative to the styrene monomer). The first reactor (CSTR) was pumped into the second reactor (PFR) at a polymerization temperature of 112 ℃ and a pressure of 0.05MPaA, at a monomer conversion of 20%. The polymerization temperature of the second reactor is 120-134 ℃, the pressure is 2.1MPaA, and when the monomer conversion rate is 45%, the reaction mixture is pumped into a third reactor (PFR) by a pump. The polymerization temperature of the third reactor is 134-155 ℃, the pressure is 1.5MPaA, and when the monomer conversion rate is 70%, the reaction mixture is pumped into a fourth reactor (PFR) by a pump; the polymerization temperature of the fourth polymerization reactor is 155-170 ℃, the pressure is 0.7MPaA, the monomer conversion rate is 83%, the copolymerization resin is obtained by removing the monomer and the solvent, and the characterization result is shown in Table 1.
Example 6
The process shown in figure 1 is adopted, the mass ratio of styrene monomer to methyl methacrylate monomer is 7:3, the solvent ethylbenzene accounts for 5 wt% of the total reaction system, and the initiator is a tetrafunctional initiator Luperox JWEB50 (commercially available) and is used in an amount of 800ppm (relative to the styrene monomer). Other conditions were the same as in example 5, and the characterization results of the obtained polymer are shown in Table 1.
TABLE 1
As can be seen from Table 1, the styrene- (meth) acrylate copolymer of the present invention has good mechanical properties, and also has high melt strength, low water absorption, and good light transmittance.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (12)
1. A styrene- (meth) acrylate copolymer comprising a structural unit A derived from a styrene-based monomer and a structural unit B derived from a (meth) acrylate-based monomer; wherein, the content of the structural unit A is 10 wt% -95 wt%, preferably 30 wt% -90 wt%, and more preferably 50 wt% -80 wt% based on the total weight of the copolymer; the content of the structural unit B is 5 wt% -90 wt%, preferably 10 wt% -70 wt%, and more preferably 20 wt% -50 wt%; and the total content of the structural unit A and the structural unit B is more than 90 wt%;
the weight average molecular weight of the copolymer is 20 ten thousand or more, preferably 25 ten thousand or more; the copolymer has a ratio of absolute molecular weight to GPC weight average molecular weight Mw.Mall/Mw.GPC ranging from 1.1 to 2.5, preferably from 1.2 to 1.5.
2. Styrene- (meth) acrylate copolymer according to claim 1, wherein the melt strength of the copolymer is 0.2-0.5N, preferably 0.24-0.4N.
3. Styrene- (meth) acrylate copolymer according to claim 1 or 2, wherein the styrenic monomer is selected from one or more of styrene, α -methylstyrene, vinyltoluene, vinylxylene, vinylethylbenzene, isobutylene styrene, tert-butylstyrene, bromostyrene, dibromostyrene, chlorostyrene and dichlorostyrene, preferably styrene.
4. The styrene- (meth) acrylate copolymer according to claim 1 or 2, wherein the (meth) acrylate-based monomer is one or more selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octadecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, preferably is methyl methacrylate.
5. A method for preparing a styrene- (meth) acrylate copolymer, the method comprising: polymerizing a styrene monomer and a (methyl) acrylate monomer under an initiator system to obtain the styrene- (methyl) acrylate copolymer; based on the total weight of the monomers, the amount of the styrene monomers is 10 wt% to 95 wt%, preferably 30 wt% to 90 wt%, and more preferably 50 wt% to 80 wt%, and the amount of the (meth) acrylate monomers is 5 wt% to 90 wt%, preferably 10 wt% to 70 wt%, and more preferably 20 wt% to 50 wt%; and the total amount of the styrene monomer and the (methyl) acrylate monomer is more than 90 wt%;
the initiator system contains a multifunctional initiator, the multifunctional initiator has more than three functional groups capable of forming free radicals, and the content of the multifunctional initiator is more than 50 wt% based on the total weight of the initiator system.
6. The production method according to claim 5, wherein the multifunctional initiator is a trifunctional peroxide initiator and/or a tetrafunctional peroxide initiator;
preferably, the multifunctional initiator is a tetrafunctional peroxide with a structure shown in a formula I or a structure shown in a formula II;
wherein R is a multifunctional nucleus, preferably cyclohexyl or dicyclohexyl propyl, and R1、R2、R3Each independently is substituted or unsubstituted C1～C5An alkyl group;
more preferably, the initiator is at least one of 2, 2-bis (4, 4-di (t-butylperoxy) cyclohexyl) propane, [6, 6-bis (5-a-bromoisobutyroyloxy-2-oxopentane) -4, 8-dioxaundecanediol 1,11] bis (a-bromoisobutyrate), and tetrabutyl peroxydicarbonate.
7. The production method according to claim 5, wherein the polymerization is a continuous bulk polymerization carried out in a plurality of reactors connected in series, and the obtained polymerization solution is devolatilized and pelletized to obtain the copolymer;
preferably, the multistage series reactor comprises a 1-3 stage fully-mixed reactor and a 1-4 stage plug flow reactor which are sequentially connected in series, and preferably comprises a 1-2 stage fully-mixed reactor and a 2-3 stage plug flow reactor which are sequentially connected in series.
8. The production process according to claim 7, wherein the continuous bulk polymerization comprises a prepolymerization stage and a polymerization stage in this order, and wherein the polymerization conversion in each reactor stage is controlled so that the polymerization conversion at the end of the prepolymerization stage is 30 to 40%.
9. The production method according to claim 8, wherein the multistage series-connected reactor comprises a four-stage reactor comprising a one-stage CSTR fully mixed reactor and a three-stage plug flow reactor connected in series in this order; wherein the content of the first and second substances,
the reaction temperature of the first-stage reactor is controlled to be 90-130 ℃, and preferably 100-120 ℃; the reaction pressure is controlled to be 0.01-5.0 MPaA, preferably 0.05-2 MPaA; when the polymerization conversion rate reaches 8-30%, preferably 15-25%, the materials in the reactor enter a second-stage reactor;
the reaction temperature of the second-stage reactor is controlled to be 100-150 ℃, and preferably controlled to be 120-140 ℃; the reaction pressure is controlled to be 0.1-10 MPaA, preferably 0.5-3 MPaA; when the polymerization conversion rate reaches 25-50%, preferably 30-40%, the materials in the reactor enter a third-stage reactor;
the reaction temperature of the third-stage reactor is controlled to be 110-180 ℃, and preferably 130-160 ℃; the reaction pressure is controlled to be 0.1-10 MPaA, preferably 0.5-3 MPaA; when the polymerization conversion rate reaches 50-70%, feeding the materials in the reactor into a fourth-stage reactor;
the reaction temperature of the fourth-stage reactor is controlled to be 120-200 ℃, and preferably 140-170 ℃; the reaction pressure is controlled to be 0.1-10 MPaA, preferably 0.5-3 MPaA; the final polymerization conversion rate is 80% or more, preferably 85% or more.
10. The preparation method according to any one of claims 5 to 9, wherein an aromatic organic solvent is included in the copolymerization system, the aromatic organic solvent is selected from at least one of benzene, toluene, xylene and ethylbenzene, and the addition amount of the aromatic organic solvent is 5 to 12 wt% of the total weight of the system;
the amount of the multifunctional initiator is 100-2000ppm, preferably 400-1500ppm, and more preferably 600-1200ppm based on the weight of the styrene monomer.
11. A styrene- (meth) acrylate copolymer produced by the production method according to any one of claims 5 to 10.
12. Use of the styrene- (meth) acrylate copolymer according to any one of claims 1 to 4 and 11 as an optical material.
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| CN114014985A (en) * | 2021-09-23 | 2022-02-08 | 万华化学(四川)有限公司 | Alpha-methylstyrene copolymer and preparation method and application thereof |
| CN116715794A (en) * | 2023-04-19 | 2023-09-08 | 天津仁泰新材料股份有限公司 | Plastic substrate master batch production process and substrate master batch |
| CN117304375A (en) * | 2023-11-08 | 2023-12-29 | 浙江信汇新材料股份有限公司 | Devolatilization method and system for isobutylene-based polymer |
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| CN114014985A (en) * | 2021-09-23 | 2022-02-08 | 万华化学(四川)有限公司 | Alpha-methylstyrene copolymer and preparation method and application thereof |
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| CN116715794A (en) * | 2023-04-19 | 2023-09-08 | 天津仁泰新材料股份有限公司 | Plastic substrate master batch production process and substrate master batch |
| CN117304375A (en) * | 2023-11-08 | 2023-12-29 | 浙江信汇新材料股份有限公司 | Devolatilization method and system for isobutylene-based polymer |
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