CN113072777A - Transparent polystyrene resin with good strength and preparation method thereof - Google Patents
Transparent polystyrene resin with good strength and preparation method thereof Download PDFInfo
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- CN113072777A CN113072777A CN202110359186.XA CN202110359186A CN113072777A CN 113072777 A CN113072777 A CN 113072777A CN 202110359186 A CN202110359186 A CN 202110359186A CN 113072777 A CN113072777 A CN 113072777A
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- 229920005990 polystyrene resin Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title description 12
- 239000000463 material Substances 0.000 claims abstract description 205
- 239000000314 lubricant Substances 0.000 claims abstract description 12
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 201
- 238000006243 chemical reaction Methods 0.000 claims description 147
- 239000003921 oil Substances 0.000 claims description 74
- 229920000642 polymer Polymers 0.000 claims description 60
- 238000001816 cooling Methods 0.000 claims description 48
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 36
- 238000001704 evaporation Methods 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 30
- 230000008020 evaporation Effects 0.000 claims description 26
- 239000000178 monomer Substances 0.000 claims description 24
- 238000005086 pumping Methods 0.000 claims description 24
- 239000003701 inert diluent Substances 0.000 claims description 16
- 239000002861 polymer material Substances 0.000 claims description 15
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 14
- 238000011084 recovery Methods 0.000 claims description 14
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 12
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 claims description 12
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 150000003568 thioethers Chemical class 0.000 claims description 8
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 6
- 239000004605 External Lubricant Substances 0.000 claims description 6
- 239000004610 Internal Lubricant Substances 0.000 claims description 6
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 6
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 235000019359 magnesium stearate Nutrition 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- 239000008116 calcium stearate Substances 0.000 claims description 4
- 235000013539 calcium stearate Nutrition 0.000 claims description 4
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- 239000012934 organic peroxide initiator Substances 0.000 claims description 4
- YSMATABRECEYRJ-UHFFFAOYSA-N tert-butyl nonaneperoxoate Chemical compound CCCCCCCCC(=O)OOC(C)(C)C YSMATABRECEYRJ-UHFFFAOYSA-N 0.000 claims description 4
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims 3
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 claims 1
- 239000004793 Polystyrene Substances 0.000 abstract description 14
- 229920002223 polystyrene Polymers 0.000 abstract description 14
- 238000004321 preservation Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 239000010779 crude oil Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a transparent polystyrene resin with good strength, which comprises the following components in parts by weight: 120 portions of 110-styrene-containing material, 0.02-3.5 portions of lubricant, 0.1-5 portions of function regulator, 0.001-0.55 portion of initiator and 0.001-7.5 portions of chain transfer agent. The invention adjusts the microstructure of the polystyrene and improves the toughness of the material, so that the polystyrene still has quite good mechanical property at lower temperature and can show better mechanical property at normal temperature, thereby meeting the application purpose of large-scale or high strength requirement.
Description
Technical Field
The invention relates to the technical field of polystyrene resin, in particular to transparent polystyrene resin with good strength and a preparation method thereof.
Background
Transparent polystyrene GPPS materials for injection molding applications are used in the production of a large number of various transparent injection molding parts. The conventional product has good light transmission and application applicability, and is easy to produce, and the general GPPS product can be produced by the process technology of producing the general GPPS product by a body method. However, the polystyrene prepared by the conventional body method and the conventional basic formula is brittle and low in strength, can only be used for preparing small injection parts, and cannot meet the application of various large injection parts with low-temperature environment resistance and high strength requirements.
Disclosure of Invention
The invention aims to provide a transparent polystyrene resin with good strength and a preparation method thereof, wherein the problem of GPPS brittleness is mainly caused by microstructure characteristics of a polystyrene material, a macromolecular chain of the polystyrene material is difficult to rotate due to the fact that a macromolecular chain is fully distributed with a benzene ring group with larger volume, the benzene ring is a non-polar group, acting force generated between molecules is not strong, and the polystyrene material has the characteristic of hardness and brittleness.
In order to achieve the above purpose, the invention provides the following technical scheme:
a transparent polystyrene resin with good strength comprises the following components in parts by weight: 120 portions of 110-styrene-containing material, 0.02-3.5 portions of lubricant, 0.1-5 portions of function regulator, 0.001-0.55 portion of initiator and 0.001-7.5 portions of chain transfer agent.
Further, the lubricant comprises an internal lubricant and an external lubricant, wherein the internal lubricant accounts for 0.01-3 parts by weight, and the external lubricant accounts for 0.01-0.5 part by weight.
Further, the internal lubricant is white oil or paraffin, and the external lubricant is stearate.
Further, the stearate is at least one of zinc stearate, calcium stearate, magnesium stearate and stearic acid amide.
Further, the function regulator is a microstructure function regulator of a leveling polymer, and the microstructure function regulator of the leveling polymer is at least one of poly-a-ph methyl styrene, divinyl benzene, ethylene glycol dimethacrylate and diallyl phthalate.
Further, the initiator is an organic peroxide initiator, and the organic peroxide initiator is at least one of tert-butyl peroxybenzoate, tert-butyl peroxypivalate, 1-di-tert-butyl peroxy-3, 3, 5-trimethylcyclohexane, 1-di-tert-butyl peroxy-cyclohexane and tert-butyl peroxynonanoate.
Further, the chain transfer agent is at least one of ethylbenzene, thioether and terpinolene.
The invention also provides a preparation method of the transparent polystyrene resin with good strength, which comprises the following steps:
1. preparing materials:
weighing materials such as styrene, a lubricant, a functional regulator, an initiator, a chain transfer agent and the like in proportion, respectively storing the materials in a preset storage tank, and conveying the materials to a preheating and prepolymerization device by using corresponding conveying equipment according to a preset flow; the feeding flow to the preheating and prepolymerization device is controlled by a gear pump or an adjusting valve controlled by frequency conversion, a flowmeter and a control system formed by the gear pump or the adjusting valve.
2. Prepolymerization reaction:
continuously and stably conveying the materials in the step 1 into a reaction kettle, controlling the temperature of the feeding material, the temperature of a jacket of the reaction kettle and the temperature of hot oil of an end socket of the reaction kettle under the conditions of 110-140 ℃, the pressure of 360-400mmHg and a stable liquid level for reaction under the condition of fully and powerfully stirring to uniformly mix the materials, and finishing the prepolymerization reaction after reacting for 2-3 hours to obtain a prepolymerization polymer;
3. post-polymerization reaction:
a. adding the pre-polymerized polymer obtained in the step 2 into a first post-polymerization kettle of a post-polymerization device for carrying out
Strong stirring, controlling the reaction temperature at 120-140 ℃, the operation pressure at 20-25Kpa and the reaction kettle full of the reactor to carry out polymerization reaction through cooling oil and a heating reactor of a jacket, finishing the first post polymerization reaction of the post polymerization reaction after 1-1.5 hours of reaction, and continuously and stably adding the material into the next-stage reaction kettle of a post polymerization device, namely a second post polymerization kettle, through a polymer delivery pump, wherein the viscosity of the material is increased;
b. the material conveyed from the first post-polymerizer of the post-polymerizer being fed to the post-polymerizer
A second post-polymerization kettle, wherein the material entering a second plug-flow polymerization reaction kettle of the post-polymerization device is subjected to polymerization reaction under the conditions of strong stirring by cooling oil of two sections of jackets and cooling oil of a coil pipe in the kettle, the reaction temperature is controlled at 140 ℃, the operation pressure is 28-33Kpa, and the reaction kettle is full of the kettle, the second post-polymerization reaction of the post-polymerization reaction is completed after 1-1.5 hours of reaction, the material is continuously and stably added into a next-stage reaction kettle of the post-polymerization device, namely a third post-polymerization kettle, and the viscosity of the material is increased again at the moment; the cooling oil through the two-stage jacket and the cooling oil of the coil in the kettle can remove the heat of reaction or heat the temperature.
c. The material conveyed from the second post-polymerizer of the post-polymerizer being fed to the post-polymerizer
A third post-polymerization kettle, wherein the material entering a third plug-flow polymerization reaction kettle of the post-polymerization device is subjected to polymerization reaction under the conditions of strong stirring by cooling oil of two sections of jackets and cooling oil of a coil pipe in the kettle, the reaction temperature is controlled at 150 ℃, the operation pressure is 38-43Kpa, and the reaction kettle is full of the kettle, the third post-polymerization reaction of the post-polymerization reaction is completed after 1-1.5 hours of reaction, and the material is continuously and stably added into a next-stage reaction kettle of the post-polymerization device, namely a fourth post-polymerization kettle, and the viscosity of the material is increased; the cooling oil through the two-stage jacket and the cooling oil of the coil in the kettle can remove the heat of reaction or heat the temperature.
d. The material conveyed from the third post-polymerizer of the post-polymerizer enters the post-polymerizer
A fourth post-polymerization kettle, wherein the material entering a fourth plug-flow polymerization reaction kettle of the post-polymerization device is subjected to polymerization reaction under the conditions of strong stirring by cooling oil of two sections of jackets and cooling oil of a coil pipe in the kettle, the reaction temperature is controlled at 170 ℃, the operation pressure is 50-55Kpa, and the reaction kettle is full of the kettle, the fourth post-polymerization reaction of the post-polymerization reaction is completed after the reaction is carried out for 1-1.5 hours, and the material is continuously and stably added into a material preheater of the de-monomer device by a polymer delivery pump; the cooling oil through the two-stage jacket and the cooling oil of the coil in the kettle can remove the heat of reaction or heat the temperature.
After the fourth post-polymerization reaction in the step 3-d, the solid content in the reaction material reaches 75-77%, the viscosity is very high, and the reaction material is continuously and stably output from a fourth post-polymerization reaction kettle of the post-polymerization device through a polymer delivery pump and enters a reaction material preheater.
4. High-temperature vacuum demonomerization:
a. in the material preheater in the step 3-d, the material is heated from the reaction temperature of 150-;
b. feeding the reactants in the step 4-a into a primary de-monolizing kettle at a feeding temperature of 220-250 ℃, controlling the pressure in the kettle to be 1.5-2.5Pa, carrying out high-temperature and low-pressure flash evaporation on the materials, evaporating more than 95% of unreacted styrene monomer, inert diluent and volatile organic matters in the primary de-monolizing kettle, pumping the evaporated materials into a recovery system by a vacuum pump, condensing and collecting, and pumping the rest materials into a secondary de-monolizing kettle by a polymer pump to enter secondary high-temperature vacuum de-monolizing; more than 95 percent of unreacted styrene monomer, inert diluent and volatile organic compounds are evaporated in the primary de-mononizing kettle, and are pumped into a recovery system by a vacuum pump for condensation and collection, at the moment, the material solvent is removed by flash evaporation, the temperature of the material is reduced by 10-20 ℃, the viscosity of the material is increased to 400000-1000000 cp, in order to ensure that the temperature of the material is not reduced too much and the viscosity is increased too much, the external part and the bottom end socket of the de-mononizing kettle are heated by adopting high-temperature hot oil for heat preservation, the material of the polymer is maintained between 220 ℃ and 240 ℃, the material has certain fluidity and can achieve good volatile removal effect, after the primary high-temperature vacuum de-mononization, the content of the residual volatilizable solvent of the obtained polymer material is reduced to about 1.25 percent, and the temperature is reduced to 200-.
c. And (3) feeding the polymer material in the first-stage monomer removing kettle in the step (4-b) into a second-stage monomer removing kettle at the temperature of 200-250 ℃, controlling the pressure in the kettle to be below 1.5Pa, carrying out high-temperature and low-pressure flash evaporation on the material, further removing 95 percent of unreacted styrene monomer, inert diluent and volatile organic matters in the second-stage monomer removing kettle, pumping the unreacted styrene monomer, the inert diluent and the volatile organic matters into a recovery system by a vacuum pump, condensing and collecting, and pumping the rest materials into a granulator through a polymer pump for granulation to obtain the polystyrene resin. 95 percent of unreacted styrene monomer, inert diluent and volatile organic compounds are further removed in the secondary de-polymerization kettle, and are pumped into a recovery system by a vacuum pump for condensation and collection, at the moment, the material solvent is removed and the temperature of the material is reduced by 3-5 ℃ due to secondary flash evaporation, so that the viscosity of the material is increased to 600000-1000000 cp, in order to ensure that the viscosity of the material is not increased too much, the external part and the bottom end socket of the de-polymerization kettle are heated by adopting high-temperature hot oil for heat preservation, the material of the polymer is maintained between 200 and 250 ℃, certain fluidity is kept and good volatile removal effect can be achieved, after secondary high-temperature vacuum de-polymerization, the content of the residual volatile solvent of the obtained polymer material is reduced to below 0.08 percent, the temperature is maintained at 200 and 250 ℃, and the viscosity is increased.
Further, in the step 4-b, when high-temperature and low-pressure flash evaporation is carried out, the outer part and the bottom end socket of the primary de-polymerization kettle are heated by adopting high-temperature hot oil for heat preservation, and the materials of the polymer are maintained between 220 ℃ and 240 ℃.
Further, in the step 4-c, when high-temperature and low-pressure flash evaporation is carried out, the external part and the bottom end socket of the secondary de-polymerization kettle are heated by adopting high-temperature hot oil for heat preservation, and the material of the polymer is maintained between 200 ℃ and 250 ℃.
The preparation method adopts the continuous plug flow bulk polymerization method with multiple serially connected kettles, obtains related experimental directional technical data through the method, optimizes the formula and process parameters of the multi-kettle serially connected large-scale product in an industrial-scale continuous plug flow bulk polymerization production device according to the guiding data obtained by the experiment, and can better obtain the transparent polystyrene resin which meets the technical characteristic requirements and is applied in market scale.
Compared with the prior art, the transparent polystyrene resin with good strength and the preparation method thereof provided by the invention have the following beneficial effects:
because the polystyrene prepared by the conventional bulk method and the conventional basic formula is brittle and low in strength, only small injection parts can be prepared, and the application of various large injection parts with low-temperature resistance and higher strength requirements cannot be met, the invention obtains partial ultrahigh molecular weight and most conventional molecular weight in the polystyrene resin according to the proportion by using a temperature control means and a molecular weight regulator means, wherein the part of the polystyrene molecules with the ultrahigh molecular weight are uniformly dispersed in the whole polymer to form skeleton-shaped distribution, thereby achieving the effect of enhancing the strength of the material, and a large number of parts with smaller molecular weight determine that the polymer can have good transparency and lower melt index, therefore, the GPPS material is improved by the technology of the invention, the formula optimization and the like, so that the GPPS material has good low-temperature resistance, and the stability of the material can be ensured even if the GPPS material is used for a long time at minus 15 ℃, therefore, the rigidity and the temperature resistance of the product meet the production requirements of large injection molding parts, and the application performance of the product is greatly improved.
The invention controls the reaction speed by using an initiator to initiate polymerization reaction, and adopts the comprehensive action of a multistage temperature control and structural function regulator and a chain transfer agent for controlling molecular weight to obtain the proportion of molecules with large molecular weight, so that the molecular weight of the polymer is distributed in a good range, wherein part of polystyrene molecules with ultra-large molecular weight are uniformly dispersed in the whole polymer to form skeleton-shaped distribution, thereby achieving the effect of enhancing the strength of the material, while a large amount of smaller molecules with conventional molecular weight determine that the polymer has good transparency and lower melt index, and the light transmittance of the product reaches more than 90.5 percent. The number average molecular weight is generally controlled to 10000-.
In addition, the lubricant molecules of the inner lubricant and the outer lubricant in the invention can be embedded between the polystyrene macromolecules in the preparation process, so that the macromolecular chain segments can slide at a certain distance after the polystyrene macromolecules are impacted by external force, thus the material has certain toughness. Meanwhile, the lubricant is matched with the viscosity-average molecular weight of the polystyrene material, so that the melt index of the material is just improved, the post-processing characteristics of the product are improved, the adding amount of the lubricant in the polystyrene is comprehensively balanced, and the strength, toughness and melt index of the polystyrene resin are well controlled, so that the transparent polystyrene resin with good strength, low temperature resistance and good processing performance is obtained, and the transparent polystyrene resin can be used for production and application of large-scale injection molding parts.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
A transparent polystyrene resin with good strength comprises the following components in parts by weight: 115 parts of styrene, 2.5 parts of white oil, 0.25 part of zinc stearate, 0.2 part of calcium stearate, 1.5 parts of poly-a-phmethylstyrene, 1.5 parts of divinylbenzene, 0.2 part of tert-butyl peroxybenzoate, 0.2 part of tert-butyl peroxypivalate, 3 parts of ethylbenzene and 3 parts of thioether.
The preparation method of the embodiment 1 comprises the following steps:
1. preparing materials:
weighing materials such as styrene, white oil, zinc stearate, calcium stearate, poly (a-phmethylstyrene), divinylbenzene, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, ethylbenzene, thioether and the like in proportion, respectively storing the materials in a preset storage tank, and conveying the materials to a preheating and prepolymerization device by using corresponding conveying equipment according to a preset flow;
2. prepolymerization reaction:
continuously and stably conveying the materials in the step (1) into a reaction kettle, controlling the temperature of the feeding material, the temperature of a jacket of the reaction kettle and the temperature of hot oil of an end socket of the reaction kettle to control the temperature in a prepolymerization kettle to react at 130 ℃, the pressure of 380mmHg and the stable liquid level under the condition of applying sufficient and powerful stirring to uniformly mix the materials, and completing prepolymerization reaction after reacting for 3 hours to obtain a prepolymerization polymer;
3. post-polymerization reaction:
a. adding the pre-polymerized polymer obtained in the step 2 into a first post-polymerization kettle of a post-polymerization device for carrying out
Performing strong stirring, controlling the reaction temperature to be 135 ℃, the operation pressure to be 20Kpa and carrying out polymerization reaction under the condition that the reaction kettle is full of the reaction kettle through cooling oil and a heating reactor of a jacket, finishing the first post polymerization reaction of the post polymerization reaction after reacting for 1.3 hours, and continuously and stably adding materials into a next-stage reaction kettle of a post polymerization device, namely a second post polymerization kettle, through a polymer delivery pump;
b. the material conveyed from the first post-polymerizer of the post-polymerizer being fed to the post-polymerizer
A second post-polymerization kettle, wherein the material entering a second plug-flow polymerization reaction kettle of the post-polymerization device is subjected to polymerization reaction under the conditions of strong stirring by cooling oil of two sections of jackets and cooling oil of a coil pipe in the kettle, the reaction temperature is controlled at 140 ℃, the operation pressure is 30Kpa, and the reaction kettle is full of the kettle, the second post-polymerization reaction of the post-polymerization reaction is completed after the reaction is carried out for 1.2 hours, and the material is continuously and stably added into a next-stage reaction kettle of the post-polymerization device, namely a third post-polymerization kettle;
c. the material conveyed from the second post-polymerizer of the post-polymerizer being fed to the post-polymerizer
A third post-polymerization kettle, wherein the material entering a third plug-flow polymerization reaction kettle of the post-polymerization device is subjected to polymerization reaction under the conditions of strong stirring by cooling oil of two sections of jackets and cooling oil of a coil pipe in the kettle, the reaction temperature is controlled at 140 ℃, the operation pressure is 40Kpa, and the reaction kettle is full of the kettle, the third post-polymerization reaction of the post-polymerization reaction is completed after the reaction is carried out for 1.2 hours, and the material is continuously and stably added into a next-stage reaction kettle of the post-polymerization device, namely a fourth post-polymerization kettle, by a polymer delivery pump;
d. the material conveyed from the third post-polymerizer of the post-polymerizer enters the post-polymerizer
A fourth post-polymerization kettle, wherein the material entering a fourth plug-flow polymerization reaction kettle of the post-polymerization device is subjected to polymerization reaction under the conditions of strong stirring by cooling oil of two sections of jackets and cooling oil of a coil pipe in the kettle, the reaction temperature is controlled at 170 ℃, the operation pressure is 50-55Kpa, and the reaction kettle is full of the kettle, the fourth post-polymerization reaction of the post-polymerization reaction is completed after the reaction is carried out for 1-1.5 hours, and the material is continuously and stably added into a material preheater of the de-monomer device by a polymer delivery pump;
after the fourth post-polymerization reaction in the step 3-d, the solid content in the reaction material reaches 77%, the viscosity is very high, and the reaction material is continuously and stably output from a fourth post-polymerization reaction kettle of the post-polymerization device through a polymer conveying pump and enters a reaction material preheater.
4. High-temperature vacuum demonomerization:
a. in the material preheater in the step 3-d, the materials are heated from the reaction temperature of 170 ℃ to the demonomerization temperature of 250 ℃ through the internal components for strengthening heat transfer in the tubes under the heating of the high-temperature crude oil, and then enter the demonomerization kettle of the next stage for demonomerization;
b. feeding the reactants in the step 4-a into a primary de-single kettle, controlling the feeding temperature to be 250 ℃, controlling the pressure in the kettle to be 2Pa, carrying out high-temperature and low-pressure flash evaporation on the materials, evaporating more than 95% of unreacted styrene monomer, inert diluent and volatile organic matters in the primary de-single kettle, pumping the materials into a recovery system by a vacuum pump, condensing and collecting, and pumping the rest materials into a secondary de-single kettle through a polymer pump to enter a secondary high-temperature vacuum de-single kettle; when high-temperature and low-pressure flash evaporation is carried out, the outside of the primary demould kettle and the bottom end socket are heated by high-temperature hot oil in a heat preservation way, and the material of the polymer is maintained between 230 ℃.
c. And 4-b, feeding the polymer material of the first-stage monomer removing kettle in the step 4-b into a second-stage monomer removing kettle, controlling the feeding temperature to be 240 ℃, controlling the pressure in the kettle to be below 1.5Pa, carrying out high-temperature and low-pressure flash evaporation on the material, further removing 95% of unreacted styrene monomer, inert diluent and volatile organic matters in the second-stage monomer removing kettle, pumping the material into a recovery system by a vacuum pump, condensing and collecting, and pumping the rest materials to a granulator through a polymer pump for granulation to obtain the polystyrene resin. When high-temperature and low-pressure flash evaporation is carried out, the outside of the secondary demould kettle and the bottom end socket are heated by high-temperature hot oil in a heat preservation way, and the material of the polymer is maintained between 230 ℃.
Example 2
A transparent polystyrene resin with good strength comprises the following components in parts by weight: 115 parts of styrene, 0.5 part of paraffin, 0.5 part of magnesium stearate, 0.5 part of stearic acid amide, 0.3 part of ethylene glycol dimethacrylate, 0.2 part of diallyl phthalate, 0.1 part of 1, 1-di-tert-butyl peroxy-3, 3, 5-trimethylcyclohexane, 1 part of thioether and 2 parts of terpinolene.
The preparation method of the embodiment 2 comprises the following steps:
1. preparing materials:
weighing materials such as styrene, paraffin, magnesium stearate, stearic acid amide, ethylene glycol dimethacrylate, diallyl phthalate, 1-di-tert-butyl peroxy-3, 5-trimethylcyclohexane, thioether and terpinolene in proportion, respectively storing the materials in a preset storage tank, and conveying the materials to a preheating and prepolymerization device by using corresponding conveying equipment according to a preset flow;
2. prepolymerization reaction:
continuously and stably conveying the materials in the step (1) into a reaction kettle, controlling the temperature of the feeding material, the temperature of a jacket of the reaction kettle and the temperature of hot oil of an end socket of the reaction kettle to control the temperature in a prepolymerization kettle to react under the conditions of 125 ℃, 370mmHg pressure and stable liquid level under the condition of applying sufficient and powerful stirring to uniformly mix the materials, and finishing prepolymerization reaction after reacting for 2 hours to obtain a prepolymerization polymer;
3. post-polymerization reaction:
a. adding the pre-polymerized polymer obtained in the step 2 into a first post-polymerization kettle of a post-polymerization device for carrying out
Performing strong stirring, controlling the reaction temperature at 130 ℃, operating pressure at 20Kpa and the condition that the reaction kettle is full of the reaction kettle through cooling oil and a heating reactor of a jacket to perform polymerization reaction, finishing the first post-polymerization reaction of the post-polymerization reaction after reacting for 1.2 hours, and continuously and stably adding the materials into a next-stage reaction kettle of a post-polymerization device, namely a second post-polymerization kettle, through a polymer delivery pump;
b. the material conveyed from the first post-polymerizer of the post-polymerizer being fed to the post-polymerizer
A second post-polymerization kettle, wherein the material entering a second plug-flow polymerization reaction kettle of the post-polymerization device is subjected to polymerization reaction under the conditions of strong stirring by cooling oil of two sections of jackets and cooling oil of a coil pipe in the kettle, the reaction temperature is controlled at 135 ℃, the operation pressure is 30Kpa, and the reaction kettle is full of the kettle, the second post-polymerization reaction of the post-polymerization reaction is completed after the reaction is carried out for 1.4 hours, and the material is continuously and stably added into a next-stage reaction kettle of the post-polymerization device, namely a third post-polymerization kettle;
c. the material conveyed from the second post-polymerizer of the post-polymerizer being fed to the post-polymerizer
A third post-polymerization kettle, wherein the material entering a third plug-flow polymerization reaction kettle of the post-polymerization device is subjected to polymerization reaction under the conditions of strong stirring by cooling oil of two sections of jackets and cooling oil of a coil pipe in the kettle, the reaction temperature is controlled at 150 ℃, the operation pressure is 40Kpa, and the reaction kettle is full of the kettle, the third post-polymerization reaction of the post-polymerization reaction is completed after the reaction is carried out for 1.3 hours, and the material is continuously and stably added into a next-stage reaction kettle of the post-polymerization device, namely a fourth post-polymerization kettle, by a polymer delivery pump;
d. the material conveyed from the third post-polymerizer of the post-polymerizer enters the post-polymerizer
A fourth post-polymerization kettle, wherein the material entering a fourth plug-flow polymerization reaction kettle of the post-polymerization device is subjected to polymerization reaction under the conditions of strong stirring by cooling oil of two sections of jackets and cooling oil of a coil pipe in the kettle, the reaction temperature is controlled at 170 ℃, the operation pressure is 50-55Kpa, and the reaction kettle is full of the kettle, the fourth post-polymerization reaction of the post-polymerization reaction is completed after the reaction is carried out for 1-1.5 hours, and the material is continuously and stably added into a material preheater of the de-monomer device by a polymer delivery pump;
after the fourth post-polymerization reaction in the step 3-d, the solid content in the reaction material reaches 76%, the viscosity is very high, and the reaction material is continuously and stably output from a fourth post-polymerization reaction kettle of the post-polymerization device through a polymer conveying pump and enters a reaction material preheater.
4. High-temperature vacuum demonomerization:
a. in the material preheater in the step 3-d, the materials are heated from the reaction temperature of 150 ℃ to the demonomerization temperature of 250 ℃ through the internal components for strengthening heat transfer in the tubes under the heating of the high-temperature crude oil, and then enter the demonomerization kettle of the next stage for demonomerization;
b. feeding the reactants in the step 4-a into a primary de-monolizing kettle, controlling the feeding temperature to be 250 ℃, controlling the pressure in the kettle to be 1.8Pa, carrying out high-temperature and low-pressure flash evaporation on the materials, evaporating more than 95% of unreacted styrene monomer, inert diluent and volatile organic matters in the primary de-monolizing kettle, pumping the evaporated materials into a recovery system by a vacuum pump, condensing and collecting, and pumping the rest materials into a secondary de-monolizing kettle by a polymer pump to enter secondary high-temperature vacuum de-monolizing; when high-temperature and low-pressure flash evaporation is carried out, the outside of the primary demould kettle and the bottom end socket are heated by high-temperature hot oil in a heat preservation way, and the material of the polymer is maintained between 230 ℃.
c. And 4-b, feeding the polymer material of the first-stage monomer removing kettle in the step 4-b into a second-stage monomer removing kettle, controlling the feeding temperature to be 210 ℃, controlling the pressure in the kettle to be below 1.5Pa, carrying out high-temperature and low-pressure flash evaporation on the material, further removing 95 percent of unreacted styrene monomer, inert diluent and volatile organic matters in the second-stage monomer removing kettle, pumping the material into a recovery system by a vacuum pump, condensing and collecting, and pumping the rest materials to a granulator through a polymer pump for granulation to obtain the polystyrene resin. When high-temperature and low-pressure flash evaporation is carried out, the outside of the secondary demould kettle and the bottom end socket are heated by high-temperature hot oil in a heat preservation way, and the temperature of the polymer material is maintained between 240 ℃.
Example 3
A transparent polystyrene resin with good strength comprises the following components in parts by weight: 110 portions of styrene, 0.01 portion of white oil, 0.01 portion of zinc stearate, 2.5 portions of poly-a-phmethylstyrene, 2.5 portions of diallyl phthalate, 0.25 portion of 1, 1 di-tert-butyl peroxy-cyclohexane, 0.3 portion of tert-butyl peroxynonanoate and 0.001 portion of ethylbenzene.
The preparation method of the embodiment 3 comprises the following steps:
1. preparing materials:
weighing styrene, white oil, zinc stearate, poly (a-phmethylstyrene), diallyl phthalate, 1 di-tert-butyl peroxy-cyclohexane, tert-butyl peroxynonanoate, ethylbenzene and other materials in proportion, respectively storing the materials in a preset storage tank, and conveying the materials to a preheating and prepolymerization device by using corresponding conveying equipment according to a preset flow;
2. prepolymerization reaction:
continuously and stably conveying the materials in the step (1) into a reaction kettle, controlling the temperature of the feeding material, the temperature of a jacket of the reaction kettle and the temperature of hot oil of an end socket of the reaction kettle to control the temperature in a prepolymerization kettle to react under the conditions of 110 ℃, 360mmHg and stable liquid level under the condition of applying sufficient and powerful stirring to uniformly mix the materials, and finishing prepolymerization reaction after reacting for 2 hours to obtain a prepolymerization polymer;
3. post-polymerization reaction:
a. adding the pre-polymerized polymer obtained in the step 2 into a first post-polymerization kettle of a post-polymerization device for carrying out
Performing strong stirring, controlling the reaction temperature at 130 ℃, operating pressure at 25Kpa and the condition that the reaction kettle is full of the reactor through cooling oil and a heating reactor of a jacket to perform polymerization reaction, finishing the first post-polymerization reaction of the post-polymerization reaction after 1 hour of reaction, and continuously and stably adding the materials into the next-stage reaction kettle of a post-polymerization device, namely a second post-polymerization kettle, through a polymer delivery pump;
b. the material conveyed from the first post-polymerizer of the post-polymerizer being fed to the post-polymerizer
A second post-polymerization kettle, wherein the material entering a second plug-flow polymerization reaction kettle of the post-polymerization device is subjected to polymerization reaction under the conditions of strong stirring by cooling oil of two sections of jackets and cooling oil of a coil pipe in the kettle, the reaction temperature is controlled at 130 ℃, the operation pressure is 33Kpa, and the reaction kettle is full of the kettle, the second post-polymerization reaction of the post-polymerization reaction is completed after the reaction is carried out for 1.5 hours, and the material is continuously and stably added into a next-stage reaction kettle of the post-polymerization device, namely a third post-polymerization kettle;
c. the material conveyed from the second post-polymerizer of the post-polymerizer being fed to the post-polymerizer
A third post-polymerization kettle, wherein the material entering a third plug-flow polymerization reaction kettle of the post-polymerization device is subjected to polymerization reaction under the conditions of strong stirring by cooling oil of two sections of jackets and cooling oil of a coil pipe in the kettle, the reaction temperature is controlled at 145 ℃, the operation pressure is 43Kpa, and the reaction kettle is full of the kettle, the third post-polymerization reaction of the post-polymerization reaction is completed after the reaction is carried out for 1.5 hours, and the material is continuously and stably added into a next-stage reaction kettle of the post-polymerization device, namely a fourth post-polymerization kettle, by a polymer delivery pump;
d. the material conveyed from the third post-polymerizer of the post-polymerizer enters the post-polymerizer
A fourth post-polymerization kettle, wherein the material entering a fourth plug-flow polymerization reaction kettle of the post-polymerization device is subjected to polymerization reaction under the conditions of strong stirring by cooling oil of two sections of jackets and cooling oil of a coil pipe in the kettle, the reaction temperature is controlled at 170 ℃, the operation pressure is 50-55Kpa, and the reaction kettle is full of the kettle, the fourth post-polymerization reaction of the post-polymerization reaction is completed after the reaction is carried out for 1-1.5 hours, and the material is continuously and stably added into a material preheater of the de-monomer device by a polymer delivery pump;
after the fourth post-polymerization reaction in the step 3-d, the solid content in the reaction material reaches 76%, the viscosity is very high, and the reaction material is continuously and stably output from a fourth post-polymerization reaction kettle of the post-polymerization device through a polymer conveying pump and enters a reaction material preheater.
4. High-temperature vacuum demonomerization:
a. in the material preheater in the step 3-d, the material is heated from the reaction temperature of 165 ℃ to the demonomerization temperature of 220 ℃ by the internal member for strengthening heat transfer in the tube nest under the heating of the high-temperature crude oil, and then enters the demonomerization kettle of the next stage for demonomerization;
b. feeding the reactants in the step 4-a into a primary de-monolizing kettle, controlling the feeding temperature to be 220 ℃, controlling the pressure in the kettle to be 2.5Pa, carrying out high-temperature and low-pressure flash evaporation on the materials, evaporating more than 95% of unreacted styrene monomer, inert diluent and volatile organic matters in the primary de-monolizing kettle, pumping the evaporated materials into a recovery system by a vacuum pump, condensing and collecting, and pumping the rest materials into a secondary de-monolizing kettle by a polymer pump to enter secondary high-temperature vacuum de-monolizing; when high-temperature and low-pressure flash evaporation is carried out, the outside of the primary demould kettle and the bottom end socket are heated by high-temperature hot oil in a heat preservation way, and the temperature of polymer materials is maintained between 240 ℃.
c. And 4-b, feeding the polymer material of the first-stage monomer removing kettle in the step 4-b into a second-stage monomer removing kettle, controlling the feeding temperature to be 200 ℃, controlling the pressure in the kettle to be below 1.5Pa, carrying out high-temperature and low-pressure flash evaporation on the material, further removing 95 percent of unreacted styrene monomer, inert diluent and volatile organic matters in the second-stage monomer removing kettle, pumping the material into a recovery system by a vacuum pump, condensing and collecting, and pumping the rest materials to a granulator through a polymer pump for granulation to obtain the polystyrene resin. When high-temperature and low-pressure flash evaporation is carried out, the outside of the secondary demould kettle and the bottom end socket are heated by high-temperature hot oil in a heat preservation way, and the temperature of the polymer material is maintained between 200 ℃.
Example 4
A transparent polystyrene resin with good strength comprises the following components in parts by weight: 120 parts of styrene, 3 parts of paraffin, 0.5 part of magnesium stearate, 0.05 part of divinyl benzene, 0.05 part of ethylene glycol dimethacrylate, 0.001 part of tert-butyl peroxybenzoate, 4.5 parts of thioether and 3 parts of terpinolene.
The preparation method of the embodiment 4 comprises the following steps:
1. preparing materials:
weighing materials such as styrene, paraffin, magnesium stearate, divinyl benzene, ethylene glycol dimethacrylate, tert-butyl peroxybenzoate, ethylbenzene, thioether, terpinolene and the like in proportion, respectively storing the materials in preset storage tanks, and conveying the materials to a preheating and prepolymerization device by using corresponding conveying equipment according to preset flow;
2. prepolymerization reaction:
continuously and stably conveying the materials in the step (1) into a reaction kettle, controlling the temperature of the feeding material, the temperature of a jacket of the reaction kettle and the temperature of hot oil of an end socket of the reaction kettle to control the temperature in a prepolymerization kettle to react at 140 ℃, the pressure of 400mmHg and the stable liquid level under the condition of fully and powerfully stirring to uniformly mix the materials, and finishing prepolymerization reaction after reacting for 3 hours to obtain a prepolymerization polymer;
3. post-polymerization reaction:
a. adding the pre-polymerized polymer obtained in the step 2 into a first post-polymerization kettle of a post-polymerization device for carrying out
Performing strong stirring, controlling the reaction temperature at 120 ℃, operating pressure at 22Kpa and the condition that the reaction kettle is full of the reactor through cooling oil and a heating reactor of a jacket to perform polymerization reaction, finishing the first post-polymerization reaction of the post-polymerization reaction after 1.5 hours of reaction, and continuously and stably adding the materials into a next-stage reaction kettle of a post-polymerization device, namely a second post-polymerization kettle, through a polymer delivery pump;
b. the material conveyed from the first post-polymerizer of the post-polymerizer being fed to the post-polymerizer
A second post-polymerization kettle, wherein the material entering a second plug-flow polymerization reaction kettle of the post-polymerization device is subjected to polymerization reaction under the conditions of strong stirring by cooling oil of two sections of jackets and cooling oil of a coil pipe in the kettle, the reaction temperature is controlled at 140 ℃, the operation pressure is 28Kpa, and the reaction kettle is full of the kettle, the second post-polymerization reaction of the post-polymerization reaction is completed after the reaction is carried out for 1 hour, and the material is continuously and stably added into a next-stage reaction kettle of the post-polymerization device, namely a third post-polymerization kettle, by a polymer delivery pump;
c. the material conveyed from the second post-polymerizer of the post-polymerizer being fed to the post-polymerizer
A third post-polymerization kettle, wherein the material entering a third plug-flow polymerization reaction kettle of the post-polymerization device is subjected to polymerization reaction under the conditions of strong stirring by cooling oil of two sections of jackets and cooling oil of a coil pipe in the kettle, the reaction temperature is controlled at 150 ℃, the operation pressure is 38Kpa, and the reaction kettle is full of the kettle, the third post-polymerization reaction of the post-polymerization reaction is completed after the reaction is carried out for 1 hour, and the material is continuously and stably added into a next-stage reaction kettle of the post-polymerization device, namely a fourth post-polymerization kettle, by a polymer delivery pump;
d. the material conveyed from the third post-polymerizer of the post-polymerizer enters the post-polymerizer
A fourth post-polymerization kettle, wherein the material entering a fourth plug-flow polymerization reaction kettle of the post-polymerization device is subjected to polymerization reaction under the conditions of strong stirring by cooling oil of two sections of jackets and cooling oil of a coil pipe in the kettle, the reaction temperature is controlled at 170 ℃, the operation pressure is 50-55Kpa, and the reaction kettle is full of the kettle, the fourth post-polymerization reaction of the post-polymerization reaction is completed after the reaction is carried out for 1-1.5 hours, and the material is continuously and stably added into a material preheater of the de-monomer device by a polymer delivery pump;
after the fourth post-polymerization reaction in the step 3-d, the solid content in the reaction material reaches 75%, the viscosity is very high, and the reaction material is continuously and stably output from a fourth post-polymerization reaction kettle of the post-polymerization device through a polymer conveying pump and enters a reaction material preheater.
4. High-temperature vacuum demonomerization:
a. in the material preheater in the step 3-d, the materials are heated from the reaction temperature of 160 ℃ to the demonomerization temperature of 240 ℃ through the internal components for strengthening heat transfer in the tubes under the heating of the high-temperature crude oil, and then enter the demonomerization kettle of the next stage for demonomerization;
b. feeding the reactants in the step 4-a into a primary de-mono kettle, controlling the feeding temperature to be 240 ℃, controlling the pressure in the kettle to be 1.5Pa, carrying out high-temperature and low-pressure flash evaporation on the materials, evaporating more than 95% of unreacted styrene monomer, inert diluent and volatile organic matters in the primary de-mono kettle, pumping the materials into a recovery system by a vacuum pump, condensing and collecting, pumping the rest materials into a secondary de-mono kettle by a polymer pump, and carrying out secondary high-temperature vacuum de-mono; when high-temperature and low-pressure flash evaporation is carried out, the outside of the primary demould kettle and the bottom end socket are heated by high-temperature hot oil in a heat preservation way, and the temperature of polymer materials is maintained between 220 ℃.
c. And 4-b, feeding the polymer material of the first-stage monomer removing kettle in the step 4-b into a second-stage monomer removing kettle, controlling the feeding temperature to be 250 ℃, controlling the pressure in the kettle to be below 1.5Pa, carrying out high-temperature and low-pressure flash evaporation on the material, further removing 95 percent of unreacted styrene monomer, inert diluent and volatile organic matters in the second-stage monomer removing kettle, pumping the material into a recovery system by a vacuum pump, condensing and collecting, and pumping the rest materials to a granulator through a polymer pump for granulation to obtain the polystyrene resin. When high-temperature and low-pressure flash evaporation is carried out, the outside of the secondary demould kettle and the bottom end socket are heated by high-temperature hot oil in a heat preservation way, and the temperature of polymer materials is maintained between 250 ℃.
The polystyrene resin products of examples 1 to 4 and the commercially available transparent polystyrene resin were tested for their aging resistance, and the results are shown in Table 1:
TABLE 1
As can be seen from Table 1, examples 1 to 4 have better strength and transparency and lower melt index than the commercially available transparent polystyrene resin.
The features of the embodiments and embodiments described above may be combined with each other without conflict.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The transparent polystyrene resin with good strength is characterized by comprising the following components in parts by weight: 120 portions of 110-styrene-containing material, 0.02-3.5 portions of lubricant, 0.1-5 portions of function regulator, 0.001-0.55 portion of initiator and 0.001-7.5 portions of chain transfer agent.
2. The transparent polystyrene resin having good strength as claimed in claim 1, wherein the lubricant comprises an internal lubricant and an external lubricant, the internal lubricant being 0.01-3 parts by weight, and the external lubricant being 0.01-0.5 parts by weight.
3. The transparent polystyrene resin having good strength as claimed in claim 2, wherein the internal lubricant is white oil or paraffin wax, and the external lubricant is stearate.
4. The transparent polystyrene resin having good strength as claimed in claim 3, wherein the stearate is at least one of zinc stearate, calcium stearate, magnesium stearate and stearic acid amide.
5. The transparent polystyrene resin with good strength as claimed in claim 1, wherein the functional modifier is a high molecular microstructure-adjusting functional modifier, and the high molecular microstructure-adjusting functional modifier is at least one of poly-a-ph methyl styrene, divinyl benzene, ethylene glycol dimethacrylate and diallyl phthalate.
6. The transparent polystyrene resin with good strength as claimed in claim 1, wherein the initiator is an organic peroxide initiator, and the organic peroxide initiator is at least one of t-butyl peroxybenzoate, t-butyl peroxypivalate, 1-di-t-butyl peroxy-3, 3, 5-trimethylcyclohexane, 1-di-t-butyl peroxy-cyclohexane and t-butyl peroxynonanoate.
7. The transparent polystyrene resin with good strength as claimed in claim 1, wherein the chain transfer agent is at least one of ethylbenzene, thioether and terpinolene.
8. A method for preparing a transparent polystyrene resin having good strength as claimed in any one of claims 1 to 7, comprising the steps of:
1. preparing materials:
weighing materials such as styrene, a lubricant, a functional regulator, an initiator, a chain transfer agent and the like in proportion, respectively storing the materials in a preset storage tank, and conveying the materials to a preheating and prepolymerization device by using corresponding conveying equipment according to a preset flow;
prepolymerization reaction:
continuously and stably conveying the materials in the step 1 into a reaction kettle, controlling the temperature of the feeding material, the temperature of a jacket of the reaction kettle and the temperature of hot oil of an end socket of the reaction kettle under the conditions of 110-140 ℃, the pressure of 360-400mmHg and a stable liquid level for reaction under the condition of fully and powerfully stirring to uniformly mix the materials, and finishing the prepolymerization reaction after reacting for 2-3 hours to obtain a prepolymerization polymer;
post-polymerization reaction:
adding the pre-polymerized polymer obtained in the step 2 into a first post-polymerization kettle of a post-polymerization device for carrying out
Strong stirring, controlling the reaction temperature at 120-140 ℃, the operation pressure at 20-25Kpa, and the reaction kettle is full of the reactor to carry out polymerization reaction by cooling oil and a heating reactor of a jacket, finishing the first post polymerization reaction of the post polymerization reaction after 1-1.5 hours of reaction, and continuously and stably adding the materials into the next-stage reaction kettle of the post polymerization device, namely a second post polymerization kettle, by a polymer delivery pump;
the material conveyed from the first post-polymerizer of the post-polymerizer being fed to the post-polymerizer
A second post-polymerization kettle, wherein the material entering a second plug-flow polymerization reaction kettle of the post-polymerization device is subjected to polymerization reaction under the conditions of strong stirring by cooling oil of two sections of jackets and cooling oil of a coil pipe in the kettle, the reaction temperature is controlled at 140 ℃, the operation pressure is 28-33Kpa, and the reaction kettle is full of the kettle, the second post-polymerization reaction of the post-polymerization reaction is completed after the reaction is carried out for 1-1.5 hours, and the material is continuously and stably added into a next-stage reaction kettle of the post-polymerization device, namely a third post-polymerization kettle;
the material conveyed from the second post-polymerizer of the post-polymerizer being fed to the post-polymerizer
A third post-polymerization kettle, wherein the material entering a third plug-flow polymerization reaction kettle of the post-polymerization device is subjected to polymerization reaction under the conditions of strong stirring by cooling oil of two sections of jackets and cooling oil of a coil pipe in the kettle, the reaction temperature is controlled at 140-150 ℃, the operation pressure is 38-43Kpa, and the reaction kettle is full of the kettle, the third post-polymerization reaction of the post-polymerization reaction is completed after the reaction is carried out for 1-1.5 hours, and the material is continuously and stably added into a next-stage reaction kettle of the post-polymerization device, namely a fourth post-polymerization kettle;
the material conveyed from the third post-polymerizer of the post-polymerizer enters the post-polymerizer
A fourth post-polymerization kettle, wherein the material entering a fourth plug-flow polymerization reaction kettle of the post-polymerization device is subjected to polymerization reaction under the conditions of strong stirring by cooling oil of two sections of jackets and cooling oil of a coil pipe in the kettle, the reaction temperature is controlled at 170 ℃, the operation pressure is 50-55Kpa, and the reaction kettle is full of the kettle, the fourth post-polymerization reaction of the post-polymerization reaction is completed after the reaction is carried out for 1-1.5 hours, and the material is continuously and stably added into a material preheater of the de-monomer device by a polymer delivery pump;
high-temperature vacuum demonomerization:
in the material preheater in the step 3-d, the material is heated from the reaction temperature of 150-;
feeding the reactants in the step 4-a into a primary de-monolizing kettle at a feeding temperature of 220-250 ℃, controlling the pressure in the kettle to be 1.5-2.5Pa, carrying out high-temperature and low-pressure flash evaporation on the materials, evaporating more than 95% of unreacted styrene monomer, inert diluent and volatile organic matters in the primary de-monolizing kettle, pumping the evaporated materials into a recovery system by a vacuum pump, condensing and collecting, and pumping the rest materials into a secondary de-monolizing kettle by a polymer pump to enter secondary high-temperature vacuum de-monolizing;
and (3) feeding the polymer material in the first-stage monomer removing kettle in the step (4-b) into a second-stage monomer removing kettle at the temperature of 200-250 ℃, controlling the pressure in the kettle to be below 1.5Pa, carrying out high-temperature and low-pressure flash evaporation on the material, further removing 95 percent of unreacted styrene monomer, inert diluent and volatile organic matters in the second-stage monomer removing kettle, pumping the unreacted styrene monomer, the inert diluent and the volatile organic matters into a recovery system by a vacuum pump, condensing and collecting, and pumping the rest materials into a granulator through a polymer pump for granulation to obtain the polystyrene resin.
9. The method as claimed in claim 8, wherein in the step 4-b, when the high-temperature and low-pressure flash evaporation is performed, the outer part of the first-stage stripper and the bottom head are heated by high-temperature hot oil to maintain the temperature of the polymer material at 220-240 ℃.
10. The method for preparing transparent polystyrene resin with good strength as claimed in claim 8, wherein in step 4-c, when high temperature and low pressure flash evaporation is performed, the external and bottom end sockets of the secondary de-monomerization reactor are heated by high temperature hot oil to maintain the polymer material at 200-250 ℃.
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| CN202110359186.XA Pending CN113072777A (en) | 2021-04-02 | 2021-04-02 | Transparent polystyrene resin with good strength and preparation method thereof |
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Application publication date: 20210706 |