CN105623133A - Biaxial oriented polystyrene composition, preparation method therefor and application of biaxial oriented polystyrene composition - Google Patents
Biaxial oriented polystyrene composition, preparation method therefor and application of biaxial oriented polystyrene composition Download PDFInfo
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- CN105623133A CN105623133A CN201410601653.5A CN201410601653A CN105623133A CN 105623133 A CN105623133 A CN 105623133A CN 201410601653 A CN201410601653 A CN 201410601653A CN 105623133 A CN105623133 A CN 105623133A
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Abstract
The invention relates to a biaxial oriented polystyrene composition, a preparation method therefor and application of the biaxial oriented polystyrene composition. The biaxial oriented polystyrene composition contains polystyrene and polystyrene grafted cis-polybutadiene rubber, wherein in the polystyrene composition, the content of a cis-polybutadiene rubber unit is 0.1-1wt% that of a styrene unit. The preparation method for the composition comprises the steps: (1) dissolving the cis-polybutadiene rubber into styrene monomers; (2) initiating the self polymerization of the styrene monomers and the grafting of the styrene monomers to the cis-polybutadiene rubber through thermal initiation or by an initiator; and (3) after the polymerization ends, removing superfluous styrene monomers, thereby obtaining the biaxial oriented polystyrene composition. The biaxial oriented polystyrene composition can serve as a base material of biaxial oriented polystyrene sheets and films, and a toughening agent is not required to be added during processing, so that the biaxial oriented polystyrene composition has an industrial application prospect.
Description
Technical field
The present invention relates to a kind of biaxially oriented polystyrene compositions, preparation method and application.
Background technology
Biaxially oriented polystyrene (BOPS) sheet material and thin film are a kind of novel " environmentally friendly packing materials " that development in recent years is got up, it has intensity height, rigidity is big, the transparency is good, easy to process, be prone to painted, seal the advantages such as reliable, with the packing articles dimensionally stable of its processing, attractive in appearance well-pressed, when packing various artwares, tourist item, food, medicine, textile, clothing and article of everyday use, hardware commodity cultural goods and being used for mess-tin, there is good looking display effect and strengthen the performance that shelf impact.
BOPS is with general purpose polystyrene (GPPS) for raw material, but owing to GPPS is hard and crisp, it is easy to fracture, and impact strength is low and have impact on application. Produce biaxially oriented polystyrene sheet material or thin film outside Present Domestic, except the specific processing technique of needs, generally will add toughener in the course of processing. In Chinese patent CN1727393A, in order to increase hot strength and the toughness of product, adopt double screw extruder, the transparent high-impact polystyrene resin of 95��97% (weight ratios) and 3��5% toughener are sufficiently stirred for, mix, then melt extrude, form sheet through chilling, then through biaxial tension, prepare BOPS thin film.
Summary of the invention
It is an object of the invention to provide one and can be directly used for preparing biaxially oriented polystyrene sheet material and thin film, and without adding the biaxially oriented polystyrene compositions of toughener in the course of processing. It is an object of the invention to be achieved through the following technical solutions.
The present invention provides a kind of biaxially oriented polystyrene compositions, and it comprises polystyrene and polystyrene graft butadiene rubber, and in described polyphenylacetylene combination, the content of butadiene rubber unit accounts for 0.1��1wt% of the content of styrene units.
Detailed description of the invention according to one, in described polyphenylacetylene combination, the content of butadiene rubber unit accounts for 0.2��0.8wt% of the content of styrene units, it is preferable that 0.3��0.5wt%.
Detailed description of the invention according to one, described butadiene rubber is low cis polybutadiene rubber, it is preferable that Star-shaped Low-cis-Polybutadiene rubber; More preferably at 25 DEG C, 5% styrene solution viscosity (abbreviation SV value) is the Star-shaped Low-cis-Polybutadiene of 10��40cP. Described low cis polybutadiene rubber can be along Isosorbide-5-Nitrae-structural content polybutadiene rubber within the scope of 30-40%, it is preferable that along Isosorbide-5-Nitrae-structural content polybutadiene rubber within the scope of 35-40%.
Preferably, in the biaxially oriented polystyrene compositions of the present invention, the viscosity-average molecular weight of polystyrene is 7��90,000.
Preferably, the particle diameter 0.08��0.2um of the rubber particles in the biaxially oriented polystyrene compositions of the present invention.
The preparation method that present invention also offers above-mentioned biaxially oriented polystyrene compositions. Described preparation method includes:
Step 1), described butadiene rubber is dissolved in styrene monomer;
Step 2), cause styrene monomer self-polymerization and grafting on butadiene rubber by thermal initiation or initiator;
Step 3), polymerization removes unnecessary styrene monomer, obtains described biaxially oriented polystyrene compositions after terminating.
According to a specific embodiment, step 1) described in the 0.1��2wt% that addition is styrene monomer addition of butadiene rubber.
According to a specific embodiment, in step 2) in, reaction condition is: first react 3��5 hours at 100 DEG C��130 DEG C, then reacts 1��3 hour at 130 DEG C��140 DEG C, reacts 2��3 hours afterwards at 140 DEG C��170 DEG C.
According to a specific embodiment, described initiator at least one in potassium peroxydisulfate, cumyl peroxide, hydrogen phosphide cumene, benzoyl peroxide or peroxide di-t-butyl, it is preferred to use hydrogen phosphide cumene. The consumption of initiator can be the 0.1wt%��2wt% of styrene monomer total amount.
Above-mentioned polymerization is optionally added into organic solvent and is diluted, and described organic solvent preferentially adopts aromatic hydrocarbons, such as toluene, dimethylbenzene or ethylo benzene etc. The consumption of organic solvent is generally 0��60wt% of styrene monomer total amount, it is preferred to 10��30wt%.
In above-mentioned radical polymerization process, additionally can also be used with some other auxiliary agent commonly understood in the industry, such as age resistor, antioxidant, concrete such as 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD); Four [3-(3,5-di-t-butyl-4-hydroxyl) phenylpropionic acid] pentaerythritol ester (1010), three (2,4-di-t-butyl) phenyl phosphites (168), distearyl pentaerythritol diphosphite (618), N-cyclohexyl-N '-phenyl paraphenylenediamine (4010), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl) phenol (2246), 3,5-di-tert-butyl-hydroxy phenyls propanoic acid octadecanol ester (1076) etc.; Heat stabilizer, concrete such as zinc stearate, lead stearate, cadmium stearate.
The whipped form that the present invention adopts can adopt anchor agitator, gate stirrer, single helix(ribbon type) agitator, double ribbon agitator, set square middle and upper part, bottom helix(ribbon type) agitator, and wherein ribbon can be single ribbon or double; two ribbon. The present invention preferentially selects set square middle and upper part, bottom ribbon combined type agitator, and stirring speed is 150��180rpm/min, it is preferred to 170��180rpm/min.
The molecular weight of polystyrene is very big to its performance impact, and viscosity-average molecular weight is lower than 50,000, then mechanical strength is very low, and molecular weight is higher than 100,000, and processing characteristics is very poor. Polymeric reaction temperature is the principal element affecting polymer molecular weight, and reaction temperature is higher, and the more, reaction rate is more fast in the active center of formation, and polymer molecular weight is more low, and reaction temperature 10 DEG C��20 DEG C molecular weight that often rise decline at double. So must telo merization temperature to control polystyrene viscosity-average molecular weight (weight average molecular weight is between 10��400,000) between 5��100,000. What the present invention carried out be aggregated at 100��170 DEG C of temperature carries out, and pressure is normal pressure.
In order to control polymer molecular weight and improve monomer conversion, the form of stage feeding polymerization can be adopted, namely select to be polymerized the corresponding time under the reaction temperature of different polymerizations, the polymerization temperature of the present invention and being chosen as of corresponding time: at 100 DEG C��130 DEG C 4 hours, 130 DEG C��140 DEG C are reacted 2 hours, and 140 DEG C��170 DEG C are reacted 1.5 hours.
The present invention also provides for above-mentioned biaxially oriented polystyrene compositions for preparing the application of biaxially oriented polystyrene sheet material and/or thin film.
The biaxially oriented polystyrene compositions of the present invention, have employed butadiene rubber MPS. Owing to the content of rubber is very low, the particle diameter of formed rubber particles is only small, so product has the excellent transparency and glossiness; There is again excellent biaxial tension performance simultaneously. The biaxially oriented polystyrene compositions of the present invention as the base material of BOPS, owing to need not add toughener in post-production process, thus can not result in the loss of product mechanical property.
The method preparing biaxially oriented polystyrene compositions provided by the invention, polymerization technique is simple, it is possible to online production on commercial plant. By biaxially oriented polystyrene compositions prepared by the method, not only maintain the advantages such as the excellent optical property of polystyrene, and there is good biaxial tension ability.
Detailed description of the invention
The invention is further illustrated by the following examples, to deepen the understanding of the present invention. Embodiment given below is to better illustrate the present invention, and the unrestricted present invention.
Physical property measurement method:
1, glossiness (60 ��) (gloss unit): test according to GB/T8807-1988;
2, light transmittance (2mm) (%): test according to GB/T2410-2008;
3, biaxial tension performance is tested: adopt two-way film balance, and sample carries out tension test test at 138 DEG C, preheating time 2min. Rate of extension during sample test respectively 50%s-1, 100%s-1, 250%s-1, 300%s-1, 600%s-1. Rate of extension is more fast, stretches film forming multiplying power more big, it was shown that the biaxial tension performance of this sample is more good.
Embodiment 1
By Star-shaped Low-cis-Polybutadiene rubber 730AX, (Asahi Kasei Corporation of Japan produces, at 25 DEG C, 5% styrene solution viscosity is 35cP) 8g, styrene (Yanshan Petrochemical production) 1700g and ethylo benzene 300g add in still, stir, swelling 8 hours, add age resistor 10760.1g.
With nitrogen by air displacement in still. Adopting the method polymerization of free radical polymerisation in bulk, initiating method adopts thermal initiation. Polymeric kettle heats up under 170rpm stir speed (S.S.), is polymerized 4 hours at 120 DEG C, is polymerized 2 hours at 130 DEG C, is polymerized 1.5 hours at 160 DEG C. Being kept stirring for speed 170rpm in polymerization process, complete polymerization process, discharge in the devolatilizer falling into 210 DEG C by the viscous body of polymerization gained, flash distillation rapidly, removes unreacted monomer and solvent ethylbenzene under vacuum conditions. Obtaining polymer 1475g after devolatilization, styrene conversion rate is 86.3%, and butadiene rubber content percentage by weight is 0.54%, and namely cooled, pelletize, sample preparation obtain sample, and physical property is measured. Acquired results is in Table 1 and table 2.
Embodiment 2
Adopting Star-shaped Low-cis-Polybutadiene rubber 4016, (Zhuhai Ao Sheng company develops, and at 25 DEG C, 5% styrene solution viscosity is 32cP) 8g, other process conditions are identical with embodiment 1.
After devolatilization polymer 1460g, styrene conversion rate is 85.4%, and butadiene rubber content percentage by weight is 0.55%, and namely cooled, pelletize, sample preparation obtain sample, and physical property is measured. Acquired results is in Table 1 and table 2.
Comparative example 1
In reaction system, being added without butadiene rubber, be only polymerized GPPS with styrene monomer, other process conditions are identical with embodiment 1. Resulting polymers 1440g after devolatilization, the conversion ratio of styrene monomer is 84.7%, and the performance indications of the final polymer of gained are in Table 1 and table 2.
Comparative example 2
Adopting linear low cis polybutadiene rubber A55AE (Shanghai Gaoqiao petro-chemical corporation produces, and at 25 DEG C, 5% styrene solution viscosity is 170cP) 8g, other process conditions are identical with embodiment 1.
After devolatilization polymer 1500g, styrene conversion rate is 87.8%, and butadiene rubber content percentage by weight is 0.53%, and namely cooled, pelletize, sample preparation obtain sample, and physical property is measured. Acquired results is in Table 1 and table 2.
Comparative example 3
Adopting linear low cis polybutadiene rubber A35AE (Shanghai Gaoqiao petro-chemical corporation produces, and at 25 DEG C, 5% styrene solution viscosity is 85cP) 8g, other process conditions are identical with embodiment 1.
After devolatilization polymer 1460g, styrene conversion rate is 85.4%, and butadiene rubber content percentage by weight is 0.55%, and namely cooled, pelletize, sample preparation obtain sample, and physical property is measured. Acquired results is in Table 1 and table 2.
Embodiment 3
Adopting Star-shaped Low-cis-Polybutadiene rubber 730AX20g, age resistor 10760.2g, other process conditions are with embodiment 1.
After devolatilization polymer 1460g, styrene conversion rate is 84.7%, and butadiene rubber content percentage by weight is 1.36%, and namely cooled, pelletize, sample preparation obtain sample, and physical property is measured. Acquired results is in Table 1 and table 2.
Embodiment 4
Adopting Star-shaped Low-cis-Polybutadiene rubber 730AX3g, age resistor 10760.1g, other process conditions are with embodiment 1. After devolatilization polymer 1480g, styrene conversion rate is 87%, and butadiene rubber content percentage by weight is 0.2%, and namely cooled, pelletize, sample preparation obtain sample, and physical property is measured. Acquired results is in Table 1 and table 2.
Embodiment 5
Adopting Star-shaped Low-cis-Polybutadiene rubber 730AX8g, age resistor 10760.1g, speed of agitator is 85rpm in the course of the polymerization process, and other process conditions are with embodiment 1.
After devolatilization polymer 1430g, styrene conversion rate is 83.6%, and butadiene rubber content percentage by weight is 0.56%, and namely cooled, pelletize, sample preparation obtain sample, and physical property is measured. Acquired results is in Table 1 and table 2.
Comparative example 4
Adopting linear low cis polybutadiene rubber A35AE8g, the speed of agitator of reaction equation is 85rpm, and other process conditions are identical with embodiment 1.
After devolatilization polymer 1435g, styrene conversion rate is 83.9%, and butadiene rubber content percentage by weight is 0.56%, and namely cooled, pelletize, sample preparation obtain sample, and physical property is measured. Acquired results is in Table 1 and table 2.
Table 1: the optical performance test result of comparative example and embodiment
| Embodiment | Rubber type, content, speed of agitator | Glossiness (60 ��) | Light transmittance % |
| Embodiment 1 | 730AX, 0.54wt%, 170rpm | 96 | 88 |
| Embodiment 2 | SN4016,0.55wt%, 170rpm | 97 | 90 |
| Comparative example 1 | Without butadiene rubber, 170rpm | 100 | 95 |
| Comparative example 2 | A55AE, 0.53wt%, 170rpm | 75 | 42 |
| Comparative example 3 | A35AE, 0.55wt%, 170rpm | 82 | 56 |
| Embodiment 3 | 730AX, 1.36wt%, 170rpm | 92 | 81 |
| Embodiment 4 | 730AX, 0.2wt%, 170rpm | 98 | 94 |
| Embodiment 5 | 730AX, 0.56wt%, 85rpm | 85 | 78 |
| Comparative example 4 | A35AE, 0.56wt%, 85rpm | 64 | 35 |
Table 2: embodiment and comparative example biaxial tension test result
The biaxially oriented polystyrene compositions of the present invention can as the base material of biaxially oriented polystyrene sheet material and thin film, it is not necessary to adds toughener in the course of processing, has prospects for commercial application.
Claims (10)
1. a biaxially oriented polystyrene compositions, it comprises polystyrene and polystyrene graft butadiene rubber, and in described polyphenylacetylene combination, the content of butadiene rubber unit accounts for 0.1��1wt% of the content of styrene units.
2. biaxially oriented polystyrene compositions according to claim 1, it is characterised in that the content of butadiene rubber unit accounts for 0.2��0.8wt% of the content of styrene units.
3. biaxially oriented polystyrene compositions according to claim 2, it is characterised in that the content of butadiene rubber unit accounts for 0.3��0.5wt% of the content of styrene units.
4. the biaxially oriented polystyrene compositions according to any one of claims 1 to 3, it is characterised in that described butadiene rubber is low cis polybutadiene rubber, it is preferable that Star-shaped Low-cis-Polybutadiene rubber.
5. biaxially oriented polystyrene compositions according to claim 4, it is characterised in that 5% styrene solution viscosity during described Star-shaped Low-cis-Polybutadiene rubber 25 DEG C is 10��40cP.
6. a preparation method for biaxially oriented polystyrene compositions as according to any one of Claims 1 to 5, including:
Step 1), described butadiene rubber is dissolved in styrene monomer;
Step 2), cause styrene monomer self-polymerization and grafting on butadiene rubber by thermal initiation or initiator;
Step 3), polymerization removes unnecessary styrene monomer, obtains described biaxially oriented polystyrene compositions after terminating.
7. preparation method according to claim 6, it is characterised in that in step 1) in, the addition of butadiene rubber is 0.1��2wt% of styrene monomer addition.
8. the preparation method according to claim 6 or 7, it is characterized in that, in step 2) in, reaction condition is: first react 3��5 hours at 100 DEG C��130 DEG C, then react 1��3 hour at 130 DEG C��140 DEG C, react 2��3 hours at 140 DEG C��170 DEG C afterwards.
9. the preparation method according to any one of claim 6��8; it is characterized in that; described initiator at least one in potassium peroxydisulfate, cumyl peroxide, hydrogen phosphide cumene, benzoyl peroxide or peroxide di-t-butyl, it is preferable that hydrogen phosphide cumene.
10. the biaxially oriented polystyrene compositions that biaxially oriented polystyrene compositions described in any one of Claims 1 to 5 or preparation method any one of claim 6��9 obtain is for preparing the application of biaxially oriented polystyrene sheet material and/or thin film.
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