CN102558738B - Application of block copolymer as plastic toughening agent - Google Patents
Application of block copolymer as plastic toughening agent Download PDFInfo
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- CN102558738B CN102558738B CN201010623634.4A CN201010623634A CN102558738B CN 102558738 B CN102558738 B CN 102558738B CN 201010623634 A CN201010623634 A CN 201010623634A CN 102558738 B CN102558738 B CN 102558738B
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Abstract
The invention relates to a block copolymer, as well as a preparation method and an application of the block copolymer as plastic toughening agent. The invention provides a tetraphene block copolymer capable of improving impact strength of high impact polystyrene (HIPS) and polypropylene (PP). When the content of the plastic toughening agent in HIPS is up to 10%, the normal temperature notch impact strength is increased by about 50-60% and the low temperature notch impact strength is increased by about 60-70%. When the content of the plastic toughening agent in PP is up to 10%, the normal temperature notch impact strength is increased by about 30-40% and the low temperature notch impact strength is increased by about 60-70%.
Description
Technical field
The present invention relates to a kind of segmented copolymer being used as plastics toughening agent, and preparation method thereof.Specifically, the present invention relates to a kind of method preparing mono vinyl aromatic monomer-conjugated diene block copolymer.This mono vinyl aromatic monomer-conjugated diene block copolymer can be used as plastics toughening agent, improves the impact strength of HIPS, PP significantly.
Background technology
High-impact polystyrene (HIPS) is a kind of material of cheap and easy to get, handling ease.But some performance of high-impact polystyrene, as shock strength can not meet the requirement of engineering plastics, therefore makes it apply to be subject to limitation to a certain extent.
Polypropylene (PP), as one of most important general-purpose plastics, has excellent over-all properties, but due to its poor toughness, particularly occurs at low temperatures is crisp, makes it apply and is restricted.
This area still needs to carry out modification to HIPS, PP, especially its toughness is improved, it is made to meet the requirement of engineering plastics application, give full play to over-all properties and the processing characteristics of its excellence simultaneously, thus make it be more widely used in fields such as packaging, household electrical appliances (as refrigerator lining and appliance shell), building and communications and transportation.
Summary of the invention
For the above-mentioned shortcoming of HIPS and PP, present inventor has performed extensive research, find by following method of the present invention, a kind of segmented copolymer that can be used as plastics toughening agent can be prepared, the impact strength of HIPS, PP can be improved with it significantly.Described segmented copolymer comprises the end block derived from mono vinyl aromatic monomer, the central block derived from conjugate diene monomer and the random copolymerization block between above-mentioned block, wherein said random copolymerization block concentration is about 5% ~ 10%, relative to total monomer quality.The normal temperature notched Izod impact strength of HIPS, when being used for HIPS toughness reinforcing, can be improved about 50 ~ 60% with the consumption of about 10wt% by described segmented copolymer; Low temperature notched shock strength improves about 60 ~ 70%.The normal temperature notched Izod impact strength of PP, when being used for PP toughness reinforcing, can be improved about 30 ~ 40% with the consumption of about 10wt% by described segmented copolymer; Low temperature notched shock strength improves about 60 ~ 70%.The present invention is based on above-mentioned discovery to be accomplished.
An object of the present invention is to provide a kind of method preparing segmented copolymer as plastics toughening agent.
Another object of the present invention is to provide a kind of segmented copolymer that can be used as plastics toughening agent.
Another object of the present invention is to provide the purposes that above-mentioned segmented copolymer is used as plastics toughening agent.
detailed Description Of The Invention
In the hereafter description of this invention, except as otherwise clearly stating, the numerical value in the application all can be considered to be modified by word " approximately ".But the present inventor as far as possible accurately reports the numerical value in embodiment, although these numerical value inevitably comprise certain error.
In this application, unless expressly excluded, concrete or preferred embodiment of the present invention can combine.In addition, every key element of the embodiment of the present application is the concrete preferred selection of the upper technical characteristic corresponding with it.If described upper technical characteristic can combine with other upper feature, then the described key element of embodiment, i.e. described preferred selection specifically, also can combine with other upper feature described.These combinations should be regarded as a part for the application's original description content.
According to an aspect of the present invention, provide a kind of preparation method that can be used as the segmented copolymer of plastics toughening agent, comprising:
A (), under the existence of single functionality organic lithium initiator, makes mono vinyl aromatic monomer be polymerized in inert solvent, until its reaction peak temperature;
B (), when the first step temperature of reaction reaches peak temperature, adds conjugate diene monomer, these conjugate diene monomers are polymerized to and substantially transform completely;
C () adds difunctionality coupling agent and carries out coupling;
D () adds terminator and optional anti-aging agent.
According to the present invention, preferred mono vinyl aromatic monomer is vinylbenzene, and preferred conjugate diene monomer is divinyl.
According to the preferred embodiments of the invention, step (b) defines random copolymerization block between mono vinyl aromatic monomer block and conjugate diene monomer block, and its content is 1% ~ 20%, is preferably 5% ~ 10%, relative to total monomer quality; Styrene block, its content is 20% ~ 40%, is preferably 25% ~ 30%, relative to total monomer quality.
In the present invention, term " reaction peak temperature " or " peak temperature " refer to the top temperature that reaction process reaches.
In the preparation process of mono vinyl aromatic monomer of the present invention-conjugate diene monomer segmented copolymer, polar compound need not be added as activator, thus simplify polymerization process, be particularly conducive to the carrying out of solvent recovery process.Certainly, in preparation process, additive polarity compound is also fine.Said polar compound can such as, for manufacturing polar compound usually used in butylbenzene copolymer, tetrahydrofuran (THF), glycol dimethyl ether, diethylene glycol dimethyl ether, TRIGLYME, tetraethyleneglycol dimethyl ether and tetramethyl quadrol etc.
According to embodiments more of the present invention, described inert solvent can be hexanaphthene, or the mixture of hexanaphthene and normal hexane.
According to embodiments more of the present invention, react in inert gas environment, described rare gas element can be conventional those in this area, as nitrogen, argon gas or helium etc.
According to embodiments more of the present invention, described single functionality organic lithium initiator can be conventional those in anionoid polymerization field, those shown in preferred formula (I),
RLi (I)
Wherein,
R is the alkyl of straight or branched, cycloalkyl or aryl.
The preferred embodiment of single functionality organic lithium initiator comprises, but be not limited to, lithium ethide, propyl lithium, isopropyl lithium, n-Butyl Lithium, s-butyl lithium, amyl group lithium, hexyl lithium, cyclohexyl lithium, phenyl lithium, aminomethyl phenyl lithium, naphthyl lithium, preferred n-Butyl Lithium or s-butyl lithium.
According to embodiments more of the present invention, in polymerization process, the consumption of initiator can depend on the size of designed molecular weight.Generally speaking, initiator amount can be every 100g monomer about 0.5 ~ 2.0mmol, preferably 1.2 ~ 1.4mmol.
According to embodiments more of the present invention, described coupling agent can be bifunctional compound, such as, but not limited to dichlorodimethylsilane, ethylene dichloride, ethylene dibromide and methylene iodide, and preferred dichlorodimethylsilane.Preferably, the consumption of coupling agent makes the mol ratio of coupling agent and organic lithium initiator be about 0.15 ~ 0.75: 1, and preferably 0.35 ~ 0.45: 1.
According to embodiments more of the present invention, described terminator can be water or alcohols, such as, can be methyl alcohol, ethanol, Virahol, preferably water.Preferably, the consumption of terminator makes the mol ratio of terminator and organic lithium initiator be about 0.1 ~ 2: 1, and preferably 0.5 ~ 1: 1.
According to embodiments more of the present invention, described anti-aging agent can be normally used phenols or amine mixture, preferably 2,6-ditertbutylparacresol (antioxidant 264), tert-butyl catechol, 2,2 '-methylene radical-bis-(4-methyl-6-tert-butylphenol) (antioxidant 2246) etc.Preferably, the add-on of anti-aging agent can be 0.5 ~ 2% weight of amount of polymers, more preferably 0.6 ~ 1.2%.
According to a further aspect in the invention, a kind of segmented copolymer can prepared by aforesaid method is provided.
According to the present invention, described segmented copolymer comprises the end block derived from mono vinyl aromatic monomer, the central block derived from conjugate diene monomer and the random copolymerization block between above-mentioned block, wherein said random copolymerization block concentration is about 5% ~ 10%, relative to total monomer quality.
According to embodiments more of the present invention, the normal temperature notched Izod impact strength of HIPS, when being used for HIPS toughness reinforcing, can be improved about 50 ~ 60% with the consumption of about 10wt% by described segmented copolymer; Low temperature notched shock strength improves about 60 ~ 70%.The normal temperature notched Izod impact strength of PP, when being used for PP toughness reinforcing, can be improved about 30 ~ 40% with the consumption of about 10wt% by described segmented copolymer; Low temperature notched shock strength improves about 60 ~ 70%.
According to another aspect of the invention, the purposes of described segmented copolymer as plastics toughening agent is provided.
According to embodiments more of the present invention, described segmented copolymer is used for toughness reinforcing height and resists polystyrene, and when consumption is 10wt%, normal temperature notched Izod impact strength improves about 50 ~ 60%; Low temperature notched shock strength improves about 60 ~ 70%.
According to embodiments more of the present invention, described segmented copolymer is used for tenacity-increased profax, and when consumption is 10wt%, normal temperature notched Izod impact strength improves about 30 ~ 40%; Low temperature notched shock strength improves about 60 ~ 70%.
Below, the present invention is further illustrated with non-limiting example.But it should be noted, it is limitation of the present invention that these embodiments should not be considered as.
Embodiment
In present specification, unless expressly stated otherwise, all parts and per-cent are all based on weight.
embodiment 1
Under high pure nitrogen protection, in 10 liters of polymeric kettles, add mixed solvent (hexanaphthene and normal hexane, weight ratio is 88: 12) 3497g, vinylbenzene 300g successively, paradigmatic system is through high-purity N
2after displacement deoxidation, add n-Butyl Lithium 0.57g and carry out the first step polyreaction.Polymerization initiating temperature is 50 DEG C, and reaction pressure is 0.1-0.3MPa.When reaction reaches peak temperature, (60 ~ 65 DEG C) add divinyl 366g and carry out second step polyreaction.Reaction reaches peak temperature (80 ~ 90 DEG C) and adds dimethyldichlorosilane(DMCS) 0.46g in backward polymeric kettle in 15 minutes, carries out linked reaction.After linked reaction terminates, add terminator water 0.15g and anti-aging agent 2,6 ditertiary butyl p cresol 4g, termination reaction.
Glue, after water vapor accumulation, obtains butadiene-styrene block copolymer product SBS-1 after mill drying.Recording molecular weight product is 14 ~ 160,000, and molecular weight distribution is 1.1 ~ 1.2, records product modification experiment data in table 1, table 2, table 3.
embodiment 2
Under high pure nitrogen protection, in 10 liters of polymeric kettles, add mixed solvent (hexanaphthene and normal hexane, weight ratio is 88: 12) 3497g, vinylbenzene 300g successively, paradigmatic system is through high-purity N
2after displacement deoxidation, add n-Butyl Lithium 0.57g and carry out the first step polyreaction.Polymerization initiating temperature is 50 DEG C, and reaction pressure is 0.1-0.3MPa.When reaction reaches peak temperature, (60 ~ 65 DEG C) add divinyl 366g and carry out second step polyreaction.Reaction reaches peak temperature (80 ~ 90 DEG C) and adds dimethyldichlorosilane(DMCS) 0.41g in backward polymeric kettle in 15 minutes, carries out linked reaction.After linked reaction terminates, add terminator water 0.15g and anti-aging agent 2,6 ditertiary butyl p cresol 4g, termination reaction.
Glue, after water vapor accumulation, obtains butadiene-styrene block copolymer product SBS-2 after mill drying.Recording molecular weight product is 13 ~ 150,000, and molecular weight distribution is 1.1 ~ 1.2, records product modification experiment data in table 1, table 2, table 3.
embodiment 3
Under high pure nitrogen protection, in 10 liters of polymeric kettles, add mixed solvent (hexanaphthene and normal hexane, weight ratio is 88: 12) 3497g, vinylbenzene 300g successively, paradigmatic system is through high-purity N
2after displacement deoxidation, add n-Butyl Lithium 0.57g and carry out the first step polyreaction.Polymerization initiating temperature is 50 DEG C, and reaction pressure is 0.1-0.3MPa.When reaction reaches peak temperature, (60 ~ 65 DEG C) add divinyl 366g and carry out second step polyreaction.Reaction reaches peak temperature (80 ~ 90 DEG C) and adds dimethyldichlorosilane(DMCS) 0.50g in backward polymeric kettle in 15 minutes, carries out linked reaction.After linked reaction terminates, add terminator water 0.15g and anti-aging agent 2,6 ditertiary butyl p cresol 4g, termination reaction.
Glue, after water vapor accumulation, obtains butadiene-styrene block copolymer product SBS-3 after mill drying.Recording molecular weight product is 15 ~ 170,000, and molecular weight distribution is 1.1 ~ 1.2, records product modification experiment data in table 1, table 2, table 3.
table 1modifying plastics evaluation test is filled a prescription
| Numbering | Base resin/SBS sample | Proportioning |
| 1# | HIPS/SBS-1 | 90％/10％ |
| 2# | HIPS/SBS-2 | 90％/10％ |
| 3# | HIPS/SBS-3 | 90％/10％ |
| 4# | PP/SBS-1 | 90％/10％ |
| 5# | PP/SBS-2 | 90％/10％ |
| 6# | PP/SBS-3 | 90％/10％ |
table 2hIPS modified test performance measured value
When plastics toughening agent of the present invention adds 10% in HIPS, normal temperature notched Izod impact strength improves about 50 ~ 60%; Low temperature notched shock strength improves about 60 ~ 70%.When plastics toughening agent of the present invention adds 10% in PP, normal temperature notched Izod impact strength improves about 30 ~ 40%; Low temperature notched shock strength improves about 60 ~ 70%.
table 3pP modified test performance measured value
When plastics toughening agent of the present invention adds 10% in PP, normal temperature notched Izod impact strength improves about 30 ~ 40%; Low temperature notched shock strength improves about 60 ~ 70%.
Although the present invention is described with regard to some embodiment, the present invention is not limited to disclosed specific embodiments or embodiment, but wishes to cover the whole improved forms in the purport of the present invention and scope that are defined by appended claims.
Claims (15)
1. segmented copolymer is as a purposes for plastics toughening agent, and wherein this segmented copolymer is prepared by the following method, and the method comprises:
A (), under the existence of single functionality organic lithium initiator, makes mono vinyl aromatic monomer be polymerized in inert solvent, until its reaction peak temperature;
B (), when the first step temperature of reaction reaches peak temperature, adds conjugate diene monomer, these conjugate diene monomers are polymerized to and transform completely;
C () adds difunctionality coupling agent and carries out linked reaction; With
D () adds terminator and optional anti-aging agent;
Wherein step (b) defines random copolymerization block between mono vinyl aromatic monomer block and conjugate diene monomer block, and its content is 5% ~ 10%, relative to total monomer quality; Mono vinyl aromatic monomer block, its content is 20% ~ 40%, relative to total monomer quality;
Wherein said segmented copolymer is used for toughness reinforcing height and resists polystyrene, and when consumption is 10wt%, normal temperature notched Izod impact strength improves 50 ~ 60%; Low temperature notched shock strength improves 60 ~ 70%; And
Described segmented copolymer is used for tenacity-increased profax, and when consumption is 10wt%, normal temperature notched Izod impact strength improves 30 ~ 40%; Low temperature notched shock strength improves 60 ~ 70%.
2. purposes according to claim 1, wherein mono vinyl aromatic monomer is vinylbenzene, and conjugate diene monomer is divinyl.
3. purposes according to claim 1, wherein mono vinyl aromatic monomer block, its content is 25% ~ 30%, relative to total monomer quality.
4. the purposes described in any one of claim 1-3, wherein said inert solvent is hexanaphthene, or the mixture of hexanaphthene and normal hexane.
5. the purposes described in any one of claim 1-3, wherein said single functionality organic lithium initiator is n-Butyl Lithium or s-butyl lithium, and its consumption is every 100g monomer 1.2 ~ 1.4mmol.
6. the purposes described in any one of claim 1-3, wherein said coupling agent is selected from dichlorodimethylsilane, ethylene dichloride, ethylene dibromide and methylene iodide.
7. purposes according to claim 6, wherein said coupling agent is dichlorodimethylsilane.
8. purposes according to claim 6, the consumption of wherein said coupling agent makes the mol ratio of coupling agent and single functionality organic lithium initiator be 0.35 ~ 0.45: 1.
9. the purposes described in any one of claim 1-3, wherein said terminator is water or alcohols.
10. purposes according to claim 9, wherein said alcohols is methyl alcohol, ethanol or Virahol.
11. purposes according to claim 9, wherein said terminator is water.
12. purposes according to claim 9, the consumption of wherein said terminator makes the mol ratio of terminator and single functionality organic lithium initiator be 0.5 ~ 1: 1.
Purposes described in 13. any one of claim 1-3, wherein said anti-aging agent is phenols or amine.
14. purposes according to claim 13, wherein said anti-aging agent is 2,6 ditertiary butyl p cresol, tert-butyl catechol or 2,2 ,-methylene radical-bis-(4-methyl-6-tert-butylphenol).
15. purposes according to claim 13, the add-on of wherein said anti-aging agent is 0.5 ~ 2% weight of amount of polymers.
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| CN104610649A (en) * | 2014-11-05 | 2015-05-13 | 新疆开瑞新环保材料有限责任公司 | Plastic toughening agent |
| CN106349441B (en) * | 2015-07-22 | 2019-09-27 | 中国石油化工股份有限公司 | A kind of butadiene-styrene block copolymer and preparation method thereof |
| CN114437405A (en) * | 2020-11-06 | 2022-05-06 | 中国石油化工股份有限公司 | SBS thermoplastic elastomer and preparation method thereof, asymmetric antioxidant composition and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4939208A (en) * | 1986-12-04 | 1990-07-03 | Labofina, S.A. | Transparent block copolymers having two monovinyl-substituted aromatic blocks of different molecular weight |
| US5436298A (en) * | 1993-09-30 | 1995-07-25 | Phillips Petroleum Company | Block copolymers of monovinylarenes and conjugated dienes and preparation thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4939208A (en) * | 1986-12-04 | 1990-07-03 | Labofina, S.A. | Transparent block copolymers having two monovinyl-substituted aromatic blocks of different molecular weight |
| US5436298A (en) * | 1993-09-30 | 1995-07-25 | Phillips Petroleum Company | Block copolymers of monovinylarenes and conjugated dienes and preparation thereof |
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