CN1182170C - Styrene, butadiene block copolymer and its using method - Google Patents
Styrene, butadiene block copolymer and its using method Download PDFInfo
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- CN1182170C CN1182170C CNB021140340A CN02114034A CN1182170C CN 1182170 C CN1182170 C CN 1182170C CN B021140340 A CNB021140340 A CN B021140340A CN 02114034 A CN02114034 A CN 02114034A CN 1182170 C CN1182170 C CN 1182170C
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- Prior art keywords
- styrene
- butadiene
- triblock copolymer
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- temperature
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title claims abstract description 18
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229920001400 block copolymer Polymers 0.000 title claims description 3
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000005187 foaming Methods 0.000 claims abstract description 11
- 239000012780 transparent material Substances 0.000 claims abstract description 9
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 33
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- 239000005977 Ethylene Substances 0.000 claims description 11
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000004156 Azodicarbonamide Substances 0.000 claims description 3
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 3
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 3
- 229920002554 vinyl polymer Polymers 0.000 abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 239000003999 initiator Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 3
- 239000006261 foam material Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 241000197194 Bulla Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 208000002352 blister Diseases 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention provides a block polymer of styrene and butadiene, which is characterized in that the block ratio of styrene to butadiene is 28 to 40: 60 to 72, the molecular weight is from 60000 to 100000, and the vinyl content is from 10 to 20%. The block polymer of styrene and butadiene is used as foaming material as well as transparent material, wherein the weight reducing ratio can reach 25 to 35%, and the light transmittance is larger than 75%. The present invention also provides a method for applying the block polymer of styrene and butadiene to foaming material and transparent material.
Description
Technical field
The present invention relates to a kind of styrene-butadiene-styrene triblock copolymer and application method thereof
Background technology
Common vinylbenzene, butadiene block copolymer (claiming the thermoplastic elastomer SBS again) are widely used in aspects such as shoemaking, asphalt modification, engineering plastic modification and tackiness agent, because of the contents of ethylene in its microtexture generally 5%～10%, melt flow rate (MFR) is less than 4g/10min (5kg sign indicating number, 200 ℃ or 190 ℃), transmittance is between 50%～75%, when being used for foam material its to pull apart tensile strength low, frothing percentage is low, foaming is fallen anharmonic ratio less than 20%, can not take into account two indexs of melt flow rate (MFR) and tensile strength simultaneously; During as transparent material, it is yellow that outward appearance is, and the transparency is poor.
At present, Finaclear K01, K02 block polymer that Fei Lipu company produces are as transparent material, but a class that belongs to k glue, hardness are greater than 99 Shao A, and block is than being 60-80/40-20, can only be as the transparent material of high rigidity, lack rubber elasticity, can not be used as foam material and elastomerics.The method of little crosslinked, the little foam process production New type of S BS material for shoes of a kind of usefulness of bibliographical information (S-TPE), its complex process, need carry out little crosslinked, control difficulty big.
Summary of the invention
The purpose of this invention is to provide a kind of styrene-butadiene-styrene triblock copolymer, when making it be used as foam material or transparent material, can take into account two indexs of melt flow rate (MFR) and tensile strength, can have the elastomeric function and the high transparency again; And provide concrete application method.
With styrene-butadiene-styrene triblock copolymer (claiming the thermoplastic elastomer SBS again) is the main body base material, and following phenomenon can appear in foaming process: low as fluidity of molten, the injection pressure height is difficult for filling with die cavity and forms substandard products; As the fluidity of molten height, then melt viscosity is low, and gas is ganged up the formation bulla easily mutually in melt, and the tensile strength of product is reduced, and produces stream limit phenomenon in moulding process.
In the production process of SBS, the molecular weight that increases SBS can improve tensile strength, but can significantly reduce the melt fluid rate, concerning type SBS, when its molecular weight is 110,000, its melt fluid rate is reduced to 0.1g/10min (5kg sign indicating number, 200 ℃) below, and the molecular weight of reduction SBS can improve the melt fluid rate, but can reduce its tensile strength, theoretical and experience all show when the molecular weight of SBS less than 50,000 the time, block among the SBS deficiency that is separated causes tensile strength sharply to descend, and can not use.The block that improves SBS can improve its tensile strength and melt flow rate (MFR) than S/B, but the cost height, and when block than S/B greater than 45/55 the time, the cold flow phenomenon can appear in SBS, its application performance decline.
By discovering, the contents of ethylene and 1 in the control SBS microtexture, the positive and negative structural content of 4 structures can make SBS present some particular performances, thereby bring some new application.When the ethylene content of SBS is 10%～20% because its side vinyl effect, when adding whipping agent, can produce effectively crosslinked, thereby can stablize the intensity of melt and help improving frothing percentage; When contents of ethylene then makes greater than 20% the time its ageing resistance descend.The content of vinyl can reach by tetrahydrofuran (THF) and the two sections polymerization temperatures of control that add calculated amount.The block of regulating SBS is than S/B and molecular weight, make its block than S/B 28～40/72～60, molecular weight is 60,000～100,000 o'clock, can make the tensile strength of SBS greater than 18MPa, melt flow rate (MFR) is greater than 5g/10min (200 ℃ of 5Kg sign indicating numbers).
28～40/72～60, molecular weight is 6～100,000 SBS to block than S/B, the scope that is separated and allows of block at segmented copolymer, and the biphase refractive index is approaching, thus make its transmittance increase.The molecular weight or the block that increase or reduce SBS outside this scope increase than the difference that all can make the biphase refractive index, cause the decline of transmittance.
28～40/72～60, molecular weight is 6～100,000 than S/B for a kind of styrene-butadiene-styrene triblock copolymer provided by the invention, its block, and contents of ethylene is 10%～20%.This product is used for foamed material, and it falls anharmonic ratio can reach 25%～35%; Transmittance＞75% can be used as transparent material.
The production method of this styrene-butadiene-styrene triblock copolymer is to be initiator (as n-Butyl Lithium, s-butyl lithium etc.) with the organic alkali metal compound; Tetrahydrofuran (THF) is a conditioning agent, and the add-on of tetrahydrofuran (THF) is: the mol ratio of tetrahydrofuran (THF)/initiator is 10～25; The hexanaphthene, tetrahydrofuran (THF), initiator, the vinylbenzene that add calculated amount in polymeric kettle carry out one-step polymerization; The 1.3-divinyl that adds calculated amount then carries out two sections polymerizations, and control reaction temperature is at 50 ℃～60 ℃; The vinylbenzene that adds calculated amount after two sections polymerizations are intact again carries out three stage polymerization, and termination reaction is condensed deliming and become product then, and polymer monomer concentration is 10%～22% (weight) in polymerization process.
The method that styrene-butadiene-styrene triblock copolymer of the present invention is applied to foamed material is:
1) by the styrene-butadiene-styrene triblock copolymer: 50 parts～70 parts, PS:10 part～15 part, naphthenic oil: 0～15 part, EVA:8 part～10 part, zinc oxide: 0～3 part, Zinic stearas: 0～2 part, oxidation inhibitor 2.6.4 (2,6 ditertiary butyl p cresol): 0～1 part, light calcium carbonate: prepare burden for 0～20 part;
2) batching is carried out the high speed blend, advance the screw rod granulation again, temperature＜200 ℃ of control high temperature section in granulation process, the temperature of low-temperature zone＞80 ℃;
3) sneak into 1.0%～2.0% AC or AD whipping agent (major ingredient is the whipping agent of azodicarbonamide) after the granulation, the situation in die head temperature 〉=180 ℃ is injected into the foaming material then, the falling anharmonic ratio and can reach 25%～35% of this foaming material.
The method that styrene-butadiene-styrene triblock copolymer of the present invention is applied to transparent material is:
With 50 parts～100 parts of styrene-butadiene-styrene triblock copolymers, the naphthenic oil or the white oil of sneaking into 0～50 part promptly can be used for directly being injection molded into transparent products through high blend, also available screw rod is a granulated into transparent pellet and is injection molded into transparent products again, the transmittance of its product＞75%.
Mechanical property is pressed SH/T 1610-95 method and is measured,
Heavily (%)=(with quality before and after the volume material foaming poor)/(with quality before the volume material foaming) * 100% falls in foaming.
Determination of light transmittance adopts GB2410-(86) standard to record on WGW photoelectricity mist degree instrument printing opacity instrument.
Use infrared measurement during the analysis of contents of ethylene
Specific embodiment
Embodiment 1
With the butyllithium is initiator, the mol ratio of tetrahydrofuran (THF) and butyllithium is 20: 1, controlling two sections polymerization temperatures is 50 ℃～60 ℃, the preparation block is 28～40/72～60 than S/B, molecular weight is 6～100,000, ethylene content is 10%～20% styrene-butadiene-styrene triblock copolymer, and its performance is as follows:
| The sample sequence number | Block compares S/B | Molecular weight (ten thousand) | Contents of ethylene (%) | Melt flow rate (MFR) (g/10min) | Tensile strength (MPa) | Transmittance (%) |
| 1 | 28/72 | 8.2 | 12 | 3.9 | 16.2 | 75 |
| 2 | 28/72 | 9.5 | 19 | 5.2 | 17.1 | 83 |
| 3 | 28/72 | 6.7 | 17 | 10.7 | 16.5 | 81 |
| 4 | 30/70 | 6.7 | 17 | 10.7 | 18.5 | 81 |
| 5 | 32/68 | 7.0 | 18 | 8.3 | 25 | 81 |
| 6 | 31/69 | 7.1 | 19 | 7.9 | 23 | 80 |
| The sample sequence number | Block compares S/B | Molecular weight (ten thousand) | Contents of ethylene (%) | Melt flow rate (MFR) (g/10min) | Tensile strength (MPa) | Transmittance (%) |
| 7 | 35/65 | 7.5 | 16 | 6.5 | 17 | 80 |
| 8 | 34/66 | 9.5 | 15 | 5.2 | 27.1 | 83 |
| 9 | 38/62 | 9.5 | 14 | 5.7 | 27.1 | 83 |
| 10 | 40/60 | 6.4 | 17 | 8.6 | 15 | 80 |
| 11 | 40/60 | 9.2 | 11 | 5.4 | 28.1 | 83 |
| 12 | 40/60 | 6.2 | 18 | 9.4 | 29.1 | 84 |
Embodiment 2
With the block ratio is 32/68, molecular weight is 7.5 ten thousand, contents of ethylene is 18% styrene-butadiene-styrene triblock copolymer: 70 parts, PS:15 part, naphthenic oil: 15 parts, zinc oxide: 1.5 parts, Zinic stearas: 0.9 part, oxidation inhibitor 2.6.4 (2, the 6-ditertbutylparacresol): prepare burden for 1 part, blend is after the twin screw granulation, the control extruder temperature is at 120 ℃～220 ℃ in the granulation process, and the whipping agent that adds 1.5% major ingredient afterwards and be azodicarbonamide foams through injection moulding machine.It falls anharmonic ratio is 35%.
Claims (3)
1. styrene-butadiene-styrene triblock copolymer, it is characterized in that block than S/B 28～40/72～60, molecular weight is 6～100,000, contents of ethylene is 10%～20%.
2. the described styrene-butadiene-styrene triblock copolymer of claim 1 is applied to the method for foamed material, it is characterized in that:
1. by the styrene-butadiene-styrene triblock copolymer: 50 parts～70 parts, PS:10 part～15 part, naphthenic oil: 0～15 part, EVA:8 part～10 part, zinc oxide: 0～3 part, Zinic stearas: 0～2 part, 2,6 ditertiary butyl p cresol: 0～1 part, light calcium carbonate: prepare burden for 0～20 part;
2. batching is carried out the high speed blend, advance the screw rod granulation again, temperature＜200 ℃ of control high temperature section in granulation process, the temperature of low-temperature zone＞80 ℃;
3. sneaking into 1.0%～2.0% major ingredient after the granulation is the whipping agent of azodicarbonamide, and the situation in die head temperature 〉=180 ℃ is injected into the foaming material then, the falling anharmonic ratio and can reach 25%～35% of this foaming material.
3. the described styrene-butadiene-styrene triblock copolymer of claim 1 is applied to the method for transparent material, it is characterized in that: with 50 parts～100 parts of vinylbenzene, butadiene block copolymers, sneak into 0～50 part naphthenic oil or white oil through high blend, directly be injection molded into transparent products or be a granulated into transparent pellet and be injection molded into transparent products again with screw rod.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021140340A CN1182170C (en) | 2002-04-04 | 2002-04-04 | Styrene, butadiene block copolymer and its using method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021140340A CN1182170C (en) | 2002-04-04 | 2002-04-04 | Styrene, butadiene block copolymer and its using method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1377905A CN1377905A (en) | 2002-11-06 |
| CN1182170C true CN1182170C (en) | 2004-12-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021140340A Expired - Lifetime CN1182170C (en) | 2002-04-04 | 2002-04-04 | Styrene, butadiene block copolymer and its using method |
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| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850711A (en) * | 2012-09-24 | 2013-01-02 | 吴江市信许塑料鞋用配套有限公司 | Preparation method of wear-resistant rubber and plastic sole materials |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101628959A (en) | 2008-07-15 | 2010-01-20 | 中国石油化工集团公司 | Foamed styrene monomer-diolefin copolymer, and preparation method and application thereof |
| TWI491628B (en) * | 2009-07-15 | 2015-07-11 | China Petro Chemical Technology Dev Company Ltd | An injectable foamed styrene monomer-diene copolymer and preparation method and use thereof |
| CN103804764A (en) * | 2012-11-05 | 2014-05-21 | 上海凯波特种电缆料厂有限公司 | Foaming elastomer outer sheath material applied to charging cable and preparation method and application thereof |
-
2002
- 2002-04-04 CN CNB021140340A patent/CN1182170C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850711A (en) * | 2012-09-24 | 2013-01-02 | 吴江市信许塑料鞋用配套有限公司 | Preparation method of wear-resistant rubber and plastic sole materials |
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| Publication number | Publication date |
|---|---|
| CN1377905A (en) | 2002-11-06 |
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