CN103319669A - Block polymer for nylon toughening and preparation method thereof - Google Patents
Block polymer for nylon toughening and preparation method thereof Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 49
- 239000004677 Nylon Substances 0.000 title claims abstract description 44
- 229920001778 nylon Polymers 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 105
- 239000000178 monomer Substances 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 28
- 238000013467 fragmentation Methods 0.000 claims abstract description 25
- 238000006062 fragmentation reaction Methods 0.000 claims abstract description 25
- 230000002441 reversible effect Effects 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 239000006184 cosolvent Substances 0.000 claims abstract description 14
- 238000004945 emulsification Methods 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 26
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 13
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229920005603 alternating copolymer Polymers 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- -1 butyl pentyl Chemical group 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 229920002521 macromolecule Polymers 0.000 claims description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 10
- 229920002292 Nylon 6 Polymers 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000003995 emulsifying agent Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 33
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 8
- RMWVYWKGXCELSW-UHFFFAOYSA-N 1-phenylethyl 2,2-dithiophen-2-ylacetate Chemical compound S1C(=CC=C1)C(C(=O)OC(C)C1=CC=CC=C1)C=1SC=CC=1 RMWVYWKGXCELSW-UHFFFAOYSA-N 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 125000005396 acrylic acid ester group Chemical group 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000012988 Dithioester Substances 0.000 description 1
- 101001121709 Homo sapiens Nyctalopin Proteins 0.000 description 1
- 102100025469 Nyctalopin Human genes 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000005022 dithioester group Chemical group 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
本发明公开的一种用于尼龙增韧的嵌段聚合物及其制备方法。将1~20重量份的大分子可逆加成断裂链转移试剂、20重量份的苯乙烯、5~30重量份的助溶剂混合均匀，缓慢加入0.05~1.0重量份的碱和100~200重量份的水，超声乳化后加入反应器，搅拌、通氮气，加热升温，加入0.06重量份的水溶性引发剂，聚合反应；加入200重量份的水，滴加40重量份的第二单体，聚合反应；加入100重量份的水，滴加20重量份的第三单体，聚合反应。破乳、干燥得到用于尼龙增韧的嵌段聚合物。本发明细乳液聚合，无外加传统乳化剂，实际分子量符合设计值，分子量分布相对较窄，与尼龙-6共混，具有很好的增韧效果，有很好的工业化前景。The invention discloses a block polymer for toughening nylon and a preparation method thereof. Mix 1-20 parts by weight of macromolecular reversible addition-fragmentation chain transfer reagent, 20 parts by weight of styrene, and 5-30 parts by weight of co-solvent, slowly add 0.05-1.0 parts by weight of alkali and 100-200 parts by weight of After ultrasonic emulsification, add the reactor, stir, pass nitrogen, heat up, add the water-soluble initiator of 0.06 weight part, polymerization reaction; Add the water of 200 weight part, drop the second monomer of 40 weight part, polymerize Reaction; add 100 parts by weight of water, dropwise add 20 parts by weight of the third monomer, and perform polymerization reaction. Demulsification and drying are used to obtain block polymers for nylon toughening. The miniemulsion polymerization of the present invention has no external traditional emulsifier, the actual molecular weight meets the design value, and the molecular weight distribution is relatively narrow. Blended with nylon-6, it has a good toughening effect and has a good industrialization prospect.
Description
技术领域technical field
本发明涉及细乳液聚合，尤其涉及一种用于尼龙增韧的嵌段聚合物及其制备方法。The invention relates to miniemulsion polymerization, in particular to a block polymer for toughening nylon and a preparation method thereof.
背景技术Background technique
工业上阴离子聚合合成的聚苯乙烯-b-聚丁二烯-b-聚苯乙烯三嵌段聚合物（SBS）作为广泛应用的热塑性弹性体，常用于与各种树脂共混以提高基体的韧性。由于SBS非极性的特征，工业应用中需采用熔融接枝的方法将极性的马来酸酐引入到SBS上，从而改善SBS与非极性树脂如尼龙之间的界面相容性，达到有效提高抗冲击强度的目的。但由于阴离子聚合反应条件苛刻、只适合非极性共轭单体等局限性，以及SBS熔融接枝马来酸酐的低效率等问题的存在。若能够通过自由基聚合这种方法实现聚合物链长的可控增长，从而既可以保持离子型聚合物控制反应的能力，又不失去自由基聚合其本身的优点。活性聚合（CLRP）是指没有不可逆链转移和链终止的聚合过程，可以非常有效得控制单体的聚合，实现分子量可控和分子量窄分布。Industrially, polystyrene-b-polybutadiene-b-polystyrene triblock polymer (SBS) synthesized by anionic polymerization is widely used as a thermoplastic elastomer, and is often used to blend with various resins to improve the matrix. toughness. Due to the non-polar characteristics of SBS, it is necessary to introduce polar maleic anhydride into SBS by melting grafting in industrial applications, so as to improve the interfacial compatibility between SBS and non-polar resins such as nylon, and achieve effective The purpose of improving the impact strength. However, due to the harsh conditions of anionic polymerization, the limitation that it is only suitable for non-polar conjugated monomers, and the low efficiency of SBS melt-grafted maleic anhydride exist. If the controllable growth of polymer chain length can be realized by free radical polymerization, the ability of ionomers to control the reaction can be maintained without losing the advantages of free radical polymerization itself. Living polymerization (CLRP) refers to a polymerization process without irreversible chain transfer and chain termination, which can effectively control the polymerization of monomers, and achieve controllable molecular weight and narrow molecular weight distribution.
细乳液聚合具备环保、低粘、易散热等优点，因此在工业生产中越来越受到重视。传统的乳化剂及助稳定剂的添加会降低产品的最终质量，需要大量的工作才能将其从聚合产物中分离。因此，一种不需要添加传统乳化剂和助稳定剂的细乳液聚合体系具备一定的实际意义。Miniemulsion polymerization has the advantages of environmental protection, low viscosity, and easy heat dissipation, so it has been paid more and more attention in industrial production. The addition of traditional emulsifiers and co-stabilizers will reduce the final quality of the product and require a lot of work to separate them from the polymerization product. Therefore, a miniemulsion polymerization system that does not need to add traditional emulsifiers and co-stabilizers has certain practical significance.
鉴于上述的两个大背景，本发明采用了二硫酯作为小分子RAFT试剂，首先在溶液体系合成马来酸酐-苯乙烯交替共聚物的大分子RAFT试剂，在此基础上，采用苯乙烯的细乳液体系聚合得到马来酸酐改性的聚苯乙烯，以此为种子乳液进行后续的丙烯酸丁酯、苯乙烯的嵌段聚合，从而完成了含有极性基团马来酸酐的SBAS三嵌段聚合物的合成。In view of above-mentioned two big backgrounds, the present invention has adopted dithioester as small molecular RAFT reagent, at first synthesizes the macromolecular RAFT reagent of maleic anhydride-styrene alternating copolymer in solution system, on this basis, adopts styrene The polystyrene modified by maleic anhydride was obtained by the polymerization of the miniemulsion system, which was used as the seed emulsion for subsequent block polymerization of butyl acrylate and styrene, thus completing the SBAS triblock containing polar group maleic anhydride Polymer Synthesis.
相较与专利ZL200910099918.5，该方法合成的聚合物中，极性基团马来酸酐所伸展的链段长度更长（大分子RAFT试剂分子量20000，马来酸酐聚合度98，苯乙烯聚合度98），在共混挤出的过程中能够更有效地伸展到尼龙基体当中，改善了嵌段聚合物与尼龙基体的相容性，具有更好的增韧效果。Compared with the patent ZL200910099918.5, in the polymer synthesized by this method, the length of the stretched segment of the polar group maleic anhydride is longer (the molecular weight of the macromolecular RAFT reagent is 20000, the degree of polymerization of maleic anhydride is 98, and the degree of polymerization of styrene 98), in the process of blending and extrusion, it can be more effectively extended into the nylon matrix, which improves the compatibility between the block polymer and the nylon matrix, and has a better toughening effect.
发明内容Contents of the invention
本发明的目的是克服现有技术的不足，提供一种用于尼龙增韧的嵌段聚合物及其制备方法。The purpose of the present invention is to overcome the deficiencies of the prior art and provide a block polymer for toughening nylon and a preparation method thereof.
用于尼龙增韧的嵌段聚合物的化学结构通式为：The general chemical structure formula of the block polymer used for nylon toughening is:
其中，n为（苯乙烯-马来酸酐）嵌段中的苯乙烯单体的数目或者（苯乙烯-马来酸酐）嵌段中的马来酸酐单体的数目，x为苯乙烯嵌段中苯乙烯单体的数目，y为丙烯酸酯嵌段中的丙烯酸酯单体的数目，z为苯乙烯嵌段中苯乙烯单体的数目，R基团为甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基，及其支链异构体。Among them, n is the number of styrene monomers in the (styrene-maleic anhydride) block or the number of maleic anhydride monomers in the (styrene-maleic anhydride) block, and x is the number of monomers in the styrene block The number of styrene monomers, y is the number of acrylate monomers in the acrylate block, z is the number of styrene monomers in the styrene block, R groups are methyl, ethyl, propyl, butyl pentyl, hexyl, heptyl, octyl, and branched chain isomers thereof.
用于尼龙增韧的嵌段聚合物的制备方法：将1～20重量份的大分子可逆加成断裂链转移试剂、20重量份的苯乙烯、5～30重量份的助溶剂混合均匀，缓慢加入0.05～1.0重量份的碱和100～200重量份的水，超声乳化后加入反应器，搅拌、通氮气，加热升温至70℃，加入0.06重量份的水溶性引发剂，聚合反应3～10小时；加入200重量份的水，滴加40重量份的第二单体，聚合反应2～5小时；加入100重量份的水，滴加20重量份的第三单体，聚合反应3～10小时，破乳、干燥得到用于尼龙增韧的嵌段聚合物。The preparation method of the block polymer used for nylon toughening: mix 1-20 parts by weight of macromolecular reversible addition fragmentation chain transfer reagent, 20 parts by weight of styrene, and 5-30 parts by weight of co-solvent, mix uniformly, slowly Add 0.05 to 1.0 parts by weight of alkali and 100 to 200 parts by weight of water, put them into the reactor after ultrasonic emulsification, stir, blow nitrogen, heat up to 70°C, add 0.06 parts by weight of water-soluble initiator, and polymerize for 3 to 10 hour; add 200 parts by weight of water, dropwise add 40 parts by weight of the second monomer, and polymerize for 2 to 5 hours; add 100 parts by weight of water, dropwise add 20 parts by weight of the third monomer, and polymerize for 3 to 10 hours Hours, demulsification and drying to obtain block polymers for nylon toughening.
所述的大分子可逆加成断裂链转移试剂是苯乙烯马来酸酐交替共聚物，化学结构通式为：The macromolecular reversible addition-fragmentation chain transfer reagent is an alternating copolymer of styrene-maleic anhydride, and its general chemical structure is:
其中，n为苯乙烯单体的数目或者马来酸酐单体的数目。Wherein, n is the number of styrene monomers or the number of maleic anhydride monomers.
所述的大分子可逆加成断裂链转移试剂的数均分子量为1000～20000的交替共聚物。所述的第一单体为苯乙烯，第二单体为丙烯酸酯类的聚合物单体，第三单体为苯乙烯。所述水溶性引发剂为过硫酸钾。The macromolecule reversible addition fragmentation chain transfer reagent is an alternating copolymer with a number average molecular weight of 1000-20000. The first monomer is styrene, the second monomer is acrylate polymer monomer, and the third monomer is styrene. The water-soluble initiator is potassium persulfate.
所述丙烯酸酯类的聚合物单体为丙烯酸酯类单体，化学结构式为：The polymer monomer of the acrylic acid ester is an acrylic acid ester monomer, and the chemical structural formula is:
R基团为甲基、乙基、丙基、丁基、戊基、已基、庚基、辛基，及其文链异构体。R groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and chain isomers thereof.
所述的碱为氨水或氢氧化钠。所述的助溶剂为丙酮。Described alkali is ammonia water or sodium hydroxide. Described cosolvent is acetone.
本发明的优点有：细乳液聚合，无外加传统乳化剂，实际分子量符合设计值，分子量分布相对较窄，与尼龙-6共混，具有很好的增韧效果，有很好的工业化前景。The invention has the advantages of: fine emulsion polymerization, no external traditional emulsifier, the actual molecular weight meets the design value, the molecular weight distribution is relatively narrow, blended with nylon-6, has a good toughening effect, and has a good industrialization prospect.
具体实施方式Detailed ways
用于尼龙增韧的嵌段聚合物的化学结构通式为：The general chemical structure formula of the block polymer used for nylon toughening is:
其中，n为（苯乙烯-马来酸酐）嵌段中的苯乙烯单体的数目或者（苯乙烯-马来酸酐）嵌段中的马来酸酐单体的数目，x为苯乙烯嵌段中苯乙烯单体的数目，y为丙烯酸酯嵌段中的丙烯酸酯单体的数目，z为苯乙烯嵌段中苯乙烯单体的数目，R基团为甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基，及其支链异构体。Among them, n is the number of styrene monomers in the (styrene-maleic anhydride) block or the number of maleic anhydride monomers in the (styrene-maleic anhydride) block, and x is the number of monomers in the styrene block The number of styrene monomers, y is the number of acrylate monomers in the acrylate block, z is the number of styrene monomers in the styrene block, R groups are methyl, ethyl, propyl, butyl pentyl, hexyl, heptyl, octyl, and branched chain isomers thereof.
用于尼龙增韧的嵌段聚合物的制备方法：将1～20重量份的大分子可逆加成断裂链转移试剂、20重量份的苯乙烯、5～30重量份的助溶剂混合均匀，缓慢加入0.05～1.0重量份的碱和100～200重量份的水，超声乳化后加入反应器，搅拌、通氮气，加热升温至70℃，加入0.06重量份的水溶性引发剂，聚合反应3～10小时；加入200重量份的水，滴加40重量份的第二单体，聚合反应2～5小时；加入100重量份的水，滴加20重量份的第三单体，聚合反应3～10小时，破乳、干燥得到用于尼龙增韧的嵌段聚合物。The preparation method of the block polymer used for nylon toughening: mix 1-20 parts by weight of macromolecular reversible addition fragmentation chain transfer reagent, 20 parts by weight of styrene, and 5-30 parts by weight of co-solvent, mix uniformly, slowly Add 0.05 to 1.0 parts by weight of alkali and 100 to 200 parts by weight of water, put them into the reactor after ultrasonic emulsification, stir, blow nitrogen, heat up to 70°C, add 0.06 parts by weight of water-soluble initiator, and polymerize for 3 to 10 hour; add 200 parts by weight of water, dropwise add 40 parts by weight of the second monomer, and polymerize for 2 to 5 hours; add 100 parts by weight of water, dropwise add 20 parts by weight of the third monomer, and polymerize for 3 to 10 hours Hours, demulsification and drying to obtain block polymers for nylon toughening.
所述的大分子可逆加成断裂链转移试剂是苯乙烯马来酸酐交替共聚物，化学结构通式为：The macromolecular reversible addition-fragmentation chain transfer reagent is an alternating copolymer of styrene-maleic anhydride, and its general chemical structure is:
其中，n为苯乙烯单体的数目或者马来酸酐单体的数目。Wherein, n is the number of styrene monomers or the number of maleic anhydride monomers.
所述的大分子可逆加成断裂链转移试剂的数均分子量为1000～20000的交替共聚物。所述的第一单体为苯乙烯，第二单体为丙烯酸酯类的聚合物单体，第三单体为苯乙烯。所述水溶性引发剂为过硫酸钾。The macromolecule reversible addition fragmentation chain transfer reagent is an alternating copolymer with a number average molecular weight of 1000-20000. The first monomer is styrene, the second monomer is acrylate polymer monomer, and the third monomer is styrene. The water-soluble initiator is potassium persulfate.
所述丙烯酸酯类的聚合物单体为丙烯酸酯类单体，化学结构式为：The polymer monomer of the acrylic acid ester is an acrylic acid ester monomer, and the chemical structural formula is:
R基团为甲基、乙基、丙基、丁基、戊基、已基、庚基、辛基，及其文链异构体。R groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and chain isomers thereof.
所述的碱为氨水或氢氧化钠。所述的助溶剂为丙酮。Described alkali is ammonia water or sodium hydroxide. Described cosolvent is acetone.
本发明实施例中所用的大分子可逆加成断裂链转移试剂化学结构简式主要有以下七种：The simplified chemical structure formulas of macromolecular reversible addition-fragmentation chain transfer reagents used in the examples of the present invention mainly include the following seven types:
大分子可逆加成断裂链转移试剂（1），由苯乙烯和马来酸酐共聚到二硫代苯乙酸-1-苯基乙酯得到，其中苯乙烯的单元数为4，马来酸酐的单元数为4。Macromolecular reversible addition-fragmentation chain transfer reagent (1), obtained by copolymerizing styrene and maleic anhydride to 1-phenylethyl dithiophenylacetate, wherein the number of units of styrene is 4, and the number of units of maleic anhydride The number is 4.
大分子可逆加成断裂链转移试剂（2），由苯乙烯和马来酸酐共聚到二硫代苯乙酸-1-苯基乙酯得到，其中苯乙烯的单元数为9，马来酸酐的单元数为9。Macromolecular reversible addition-fragmentation chain transfer reagent (2), obtained by copolymerizing styrene and maleic anhydride to 1-phenylethyl dithiophenylacetate, wherein the number of units of styrene is 9, and the number of units of maleic anhydride The number is 9.
大分子可逆加成断裂链转移试剂（3），由苯乙烯和马来酸酐共聚到二硫代苯乙酸-1-苯基乙酯得到，其中苯乙烯的单元数为13，马来酸酐的单元数为13。Macromolecular reversible addition-fragmentation chain transfer reagent (3), obtained by copolymerizing styrene and maleic anhydride to 1-phenylethyl dithiophenylacetate, wherein the number of units of styrene is 13, and the number of units of maleic anhydride The number is 13.
大分子可逆加成断裂链转移试剂（4），由苯乙烯和马来酸酐共聚到二硫代苯乙酸-1-苯基乙酯得到，其中苯乙烯的单元数为24，马来酸酐的单元数为24。Macromolecular reversible addition-fragmentation chain transfer reagent (4), obtained by copolymerizing styrene and maleic anhydride to 1-phenylethyl dithiophenylacetate, wherein the number of units of styrene is 24, and the number of units of maleic anhydride The number is 24.
大分子可逆加成断裂链转移试剂（5），由苯乙烯和马来酸酐共聚到二硫代苯乙酸-1-苯基乙酯得到，其中苯乙烯的单元数为50，马来酸酐的单元数为50。Macromolecular reversible addition-fragmentation chain transfer reagent (5), obtained by copolymerizing styrene and maleic anhydride to 1-phenylethyl dithiophenylacetate, wherein the number of units of styrene is 50, and the number of units of maleic anhydride The number is 50.
大分子可逆加成断裂链转移试剂（6），由苯乙烯和马来酸酐共聚到二硫代苯乙酸-1-苯基乙酯得到，其中苯乙烯的单元数为74，马来酸酐的单元数为74。Macromolecular reversible addition-fragmentation chain transfer reagent (6), obtained by copolymerizing styrene and maleic anhydride to 1-phenylethyl dithiophenylacetate, wherein the number of units of styrene is 74, and the number of units of maleic anhydride The number is 74.
大分子可逆加成断裂链转移试剂（7），由苯乙烯和马来酸酐共聚到二硫代苯乙酸-1-苯基乙酯得到，其中苯乙烯的单元数为98，马来酸酐的单元数为98。Macromolecular reversible addition-fragmentation chain transfer reagent (7), obtained by copolymerizing styrene and maleic anhydride to 1-phenylethyl dithiophenylacetate, wherein the number of units of styrene is 98, and the number of units of maleic anhydride The number is 98.
实施例1：Example 1:
将1克的大分子可逆加成断裂链转移试剂（1）、20克的苯乙烯、5克的助溶剂混合均匀，缓慢加入0.05克的氨水和100克的水，超声乳化后加入反应器，搅拌、通氮气，加热升温至70℃，加入0.06克的过硫酸钾，聚合反应3小时；加入200克的水，滴加40克的丙烯酸丁酯，聚合反应2小时；加入100克的水，滴加20克的苯乙烯，聚合反应3小时。破乳、干燥得到用于尼龙增韧的嵌段聚合物（1）。Mix 1 gram of macromolecular reversible addition-fragmentation chain transfer reagent (1), 20 grams of styrene, and 5 grams of cosolvent, slowly add 0.05 grams of ammonia water and 100 grams of water, and add them to the reactor after ultrasonic emulsification. Stir, blow nitrogen, heat up to 70°C, add 0.06 grams of potassium persulfate, and polymerize for 3 hours; add 200 grams of water, dropwise add 40 grams of butyl acrylate, and polymerize for 2 hours; add 100 grams of water, 20 g of styrene was added dropwise, and the polymerization was carried out for 3 hours. The block polymer (1) for nylon toughening is obtained by demulsification and drying.
实施例2：Example 2:
将2克的大分子可逆加成断裂链转移试剂（2）、20克的苯乙烯、10克的助溶剂混合均匀，缓慢加入0.1克的氨水和105克的水，超声乳化后加入反应器，搅拌、通氮气，加热升温至70℃，加入0.06克的过硫酸钾，聚合反应4小时；加入200克的水，滴加40克的丙烯酸丁酯，聚合反应3小时；加入100克的水，滴加20克的苯乙烯，聚合反应4小时。破乳、干燥得到用于尼龙增韧的嵌段聚合物（2）。Mix 2 grams of macromolecular reversible addition-fragmentation chain transfer reagent (2), 20 grams of styrene, and 10 grams of cosolvent, slowly add 0.1 grams of ammonia and 105 grams of water, and add them to the reactor after ultrasonic emulsification. Stir, blow nitrogen, heat up to 70°C, add 0.06 grams of potassium persulfate, and polymerize for 4 hours; add 200 grams of water, dropwise add 40 grams of butyl acrylate, and polymerize for 3 hours; add 100 grams of water, 20 g of styrene was added dropwise, and the polymerization was carried out for 4 hours. The block polymer (2) for toughening nylon is obtained by demulsification and drying.
实施例3：Example 3:
将3克的大分子可逆加成断裂链转移试剂（3）、20克的苯乙烯、10克的助溶剂混合均匀，缓慢加入0.15克的氨水和110克的水，超声乳化后加入反应器，搅拌、通氮气，加热升温至70℃，加入0.06克的过硫酸钾，聚合反应4小时；加入200克的水，滴加40克的丙烯酸丁酯，聚合反应3小时；加入100克的水，滴加20克的苯乙烯，聚合反应4小时。破乳、干燥得到用于尼龙增韧的嵌段聚合物（3）。Mix 3 grams of macromolecular reversible addition-fragmentation chain transfer reagent (3), 20 grams of styrene, and 10 grams of cosolvent, slowly add 0.15 grams of ammonia and 110 grams of water, and put them into the reactor after ultrasonic emulsification. Stir, blow nitrogen, heat up to 70°C, add 0.06 grams of potassium persulfate, and polymerize for 4 hours; add 200 grams of water, dropwise add 40 grams of butyl acrylate, and polymerize for 3 hours; add 100 grams of water, 20 g of styrene was added dropwise, and the polymerization was carried out for 4 hours. The block polymer (3) for toughening nylon is obtained by demulsification and drying.
实施例4：Example 4:
将5克的大分子可逆加成断裂链转移试剂（4）、20克的苯乙烯、15克的助溶剂混合均匀，缓慢加入0.15克的氨水和120克的水，超声乳化后加入反应器，搅拌、通氮气，加热升温至70℃，加入0.06克的过硫酸钾，聚合反应5小时；加入200克的水，加入40克的丙烯酸丁酯，聚合反应3小时；加入100克的水，滴加20克的苯乙烯，聚合反应5小时。破乳、干燥得到用于尼龙增韧的嵌段聚合物（4）。Mix 5 grams of macromolecular reversible addition-fragmentation chain transfer reagent (4), 20 grams of styrene, and 15 grams of cosolvent, slowly add 0.15 grams of ammonia and 120 grams of water, and add them to the reactor after ultrasonic emulsification. Stir, blow nitrogen, heat up to 70°C, add 0.06 grams of potassium persulfate, and polymerize for 5 hours; add 200 grams of water, add 40 grams of butyl acrylate, and polymerize for 3 hours; add 100 grams of water, drip Add 20 grams of styrene, and polymerize for 5 hours. The block polymer (4) for nylon toughening is obtained by demulsification and drying.
实施例5：Example 5:
将10克的大分子可逆加成断裂链转移试剂（5）、20克的苯乙烯、20克的助溶剂混合均匀，缓慢加入0.5克的氨水和145克的水，超声乳化后加入反应器，搅拌、通氮气，加热升温至70℃，加入0.06克的过硫酸钾，聚合反应6小时；加入200克的水，滴加40克的丙烯酸丁酯，聚合反应3小时；加入100克的水，滴加20克的苯乙烯，聚合反应6小时。破乳、干燥得到用于尼龙增韧的嵌段聚合物（5）。Mix 10 grams of macromolecular reversible addition-fragmentation chain transfer reagent (5), 20 grams of styrene, and 20 grams of cosolvent, slowly add 0.5 grams of ammonia and 145 grams of water, and add them to the reactor after ultrasonic emulsification. Stir, blow nitrogen, heat up to 70°C, add 0.06 grams of potassium persulfate, and polymerize for 6 hours; add 200 grams of water, dropwise add 40 grams of butyl acrylate, and polymerize for 3 hours; add 100 grams of water, 20 g of styrene was added dropwise, and the polymerization was carried out for 6 hours. The block polymer (5) for nylon toughening is obtained by demulsification and drying.
实施例6：Embodiment 6:
将15克的大分子可逆加成断裂链转移试剂（6）、20克的苯乙烯、25克的助溶剂混合均匀，缓慢加入0.75克的氨水和170克的水，超声乳化后加入反应器，搅拌、通氮气，加热升温至70℃，加入0.06克的过硫酸钾，聚合反应8小时；加入200克的水，滴加40克的丙烯酸丁酯，聚合反应4小时；加入100克的水，滴加20克的苯乙烯，聚合反应8小时。破乳、干燥得到用于尼龙增韧的嵌段聚合物（6）。Mix 15 grams of macromolecular reversible addition-fragmentation chain transfer reagent (6), 20 grams of styrene, and 25 grams of cosolvent, slowly add 0.75 grams of ammonia and 170 grams of water, and add them to the reactor after ultrasonic emulsification. Stir, blow nitrogen, heat up to 70°C, add 0.06 grams of potassium persulfate, and polymerize for 8 hours; add 200 grams of water, dropwise add 40 grams of butyl acrylate, and polymerize for 4 hours; add 100 grams of water, 20 g of styrene was added dropwise, and the polymerization was carried out for 8 hours. The block polymer (6) for toughening nylon is obtained by demulsification and drying.
实施例7：Embodiment 7:
将20克的大分子可逆加成断裂链转移试剂（7）、20克的苯乙烯、30克的助溶剂混合均匀，缓慢加入1.0克的氨水和200克的水，超声乳化后加入反应器，搅拌、通氮气，加热升温至70℃，加入0.06克的过硫酸钾，聚合反应10小时；加入200克的水，滴加40克的丙烯酸丁酯，聚合反应5小时；加入100克的水，滴加20克的苯乙烯，聚合反应10小时。破乳、干燥得到用于尼龙增韧的嵌段聚合物（7）。Mix 20 grams of macromolecular reversible addition-fragmentation chain transfer reagent (7), 20 grams of styrene, and 30 grams of cosolvent, slowly add 1.0 grams of ammonia and 200 grams of water, and put them into the reactor after ultrasonic emulsification. Stir, blow nitrogen, heat up to 70°C, add 0.06 grams of potassium persulfate, and polymerize for 10 hours; add 200 grams of water, dropwise add 40 grams of butyl acrylate, and polymerize for 5 hours; add 100 grams of water, 20 g of styrene was added dropwise, and the polymerization was carried out for 10 hours. The block polymer (7) for toughening nylon is obtained by demulsification and drying.
反应各步骤的转化率：The conversion rate of each step of the reaction:
所得聚合物的分子量和分子量分布：Molecular weight and molecular weight distribution of the obtained polymer:
将上述所合成的用于尼龙增韧的嵌段聚合物(1)、用于尼龙增韧的嵌段聚合物(2)、用于尼龙增韧的嵌段聚合物(3)、用于尼龙增韧的嵌段聚合物(4)、用于尼龙增韧的嵌段聚合物(5)、用于尼龙增韧的嵌段聚合物(6)和用于尼龙增韧的嵌段聚合物(7)按如下配方和工艺条件与尼龙6（牌号1013B）共混，得到共混物(1)，共混物(2)，共混物(3)，共混物(4)，共混物(5)，共混物(6)和共混物(7)。The above synthesized block polymer (1) for nylon toughening, block polymer (2) for nylon toughening, block polymer (3) for nylon toughening, and nylon toughening Toughened block polymers (4), block polymers for nylon toughening (5), block polymers for nylon toughening (6) and block polymers for nylon toughening ( 7) Blend with nylon 6 (grade 1013B) according to the following formula and process conditions to obtain blend (1), blend (2), blend (3), blend (4), blend (5), blend (6) and blend (7).
配方：formula:
用于尼龙增韧的嵌段聚合物200gBlock polymer for nylon toughening 200g
尼龙6800gNylon 6800g
制备：preparation:
用于尼龙增韧的嵌段聚合物和尼龙6按照精密进样机，以质量比1:4（用于尼龙增韧的嵌段聚合物含量20%）加入双螺杆挤出机进行共混，长径比48:1，螺杆直径22mm，空气冷却，造粒。The block polymer used for nylon toughening and nylon 6 are added to the twin-screw extruder for blending at a mass ratio of 1:4 (the content of block polymer used for nylon toughening is 20%) according to the precision injection machine. Length-to-diameter ratio 48:1, screw diameter 22mm, air cooling, granulation.
工艺条件：Process conditions:
第一段80℃、第二段250℃、第三段250℃、第四段255℃、第五段255℃，模头温度240℃。The first section is 80°C, the second section is 250°C, the third section is 250°C, the fourth section is 255°C, the fifth section is 255°C, and the die head temperature is 240°C.
螺杆转速180转/分。The screw speed is 180 rpm.
将共混物(1)，共混物(2)，共混物(3)，共混物(4)，共混物(5)，共混物(6)、共混物(7)和纯尼龙-6注塑，得到标准样条进行抗冲击强度的测试（简支梁，GB/T1043-1993），测试结果如下表所示：Blend (1), blend (2), blend (3), blend (4), blend (5), blend (6), blend (7) and Pure nylon-6 is injected, and the standard sample is obtained for the impact strength test (charpy beam, GB/T1043-1993). The test results are shown in the following table:
抗冲击强度数据表明，所述用于尼龙增韧的嵌段聚合物与纯尼龙共混，具有显著的增韧效果。The impact strength data show that the block polymer used for nylon toughening is blended with pure nylon, which has a significant toughening effect.
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