CN115449018A - Maleic anhydride grafted modified ABS resin material extruded by double screw reaction and preparation method thereof - Google Patents
Maleic anhydride grafted modified ABS resin material extruded by double screw reaction and preparation method thereof Download PDFInfo
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 16
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000003999 initiator Substances 0.000 claims abstract description 40
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 37
- 150000003254 radicals Chemical class 0.000 claims abstract description 29
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000011344 liquid material Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims 1
- 150000001451 organic peroxides Chemical class 0.000 claims 1
- 239000005060 rubber Substances 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 35
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 34
- 230000009471 action Effects 0.000 abstract description 20
- 229920000578 graft copolymer Polymers 0.000 abstract description 14
- 229920007019 PC/ABS Polymers 0.000 abstract description 6
- 239000000956 alloy Substances 0.000 abstract description 6
- 229910045601 alloy Inorganic materials 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 12
- 230000000977 initiatory effect Effects 0.000 description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 9
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 239000012467 final product Substances 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
- 239000012934 organic peroxide initiator Substances 0.000 description 1
- 239000012994 photoredox catalyst Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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- 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
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
技术领域technical field
本发明属于高分子材料技术领域，具体涉及一种双螺杆反应挤出马来酸酐接枝改性ABS树脂材料及其制备方法。The invention belongs to the technical field of polymer materials, and in particular relates to a twin-screw reactive extrusion maleic anhydride graft-modified ABS resin material and a preparation method thereof.
背景技术Background technique
ABS(丙烯腈/丁二烯/苯乙烯共聚物)作为重要的工程塑料具有优异的力学性能，但是ABS的缺点在于耐热性较差，为改善ABS的耐热性，通常将ABS与聚碳酸酯PC共同改性，形成PC/ABS合金，PC/ABS合金相比ABS具有更优异的耐热性和冲击性能，但是ABS树脂与PC树脂的相容性较差，如果不添加相容剂则二者在共混过程中很难做到良好的分散，从而影响最终PC/ABS合金材料的力学性能。As an important engineering plastic, ABS (acrylonitrile/butadiene/styrene copolymer) has excellent mechanical properties, but the disadvantage of ABS is that it has poor heat resistance. In order to improve the heat resistance of ABS, ABS is usually combined with polycarbonate Co-modified with ester PC to form PC/ABS alloy, PC/ABS alloy has better heat resistance and impact performance than ABS, but the compatibility between ABS resin and PC resin is poor, if no compatibilizer is added The two are difficult to achieve good dispersion during the blending process, thus affecting the mechanical properties of the final PC/ABS alloy material.
PC/ABS合金材料最常用的相容剂是ABS接枝马来酸酐，传统生产方法是通过双螺杆挤出机进行反应接枝改性，ABS树脂与马来酸酐单体在自由基引发剂的作用下在双螺杆挤出机中进行熔融接枝反应，这种生产工艺的缺陷在于由于马来酸酐反应活性较低，导致最终马来酸酐接枝率非常低，而产品中游离马来酸酐的含量特别高，无法满足使用要求。The most commonly used compatibilizer for PC/ABS alloy materials is ABS grafted maleic anhydride. The traditional production method is to carry out reaction grafting modification through a twin-screw extruder. Carry out melt grafting reaction in twin-screw extruder under action, the defective of this production technique is because maleic anhydride reactivity is low, causes final maleic anhydride grafting rate to be very low, and the free maleic anhydride in the product The content is particularly high and cannot meet the requirements for use.
发明内容Contents of the invention
针对现有技术的不足，本发明采用高长径比的双螺杆挤出机作为反应器，不添加任何溶剂，以丁苯橡胶(SBR)为基体聚合物，苯乙烯(St)单体、马来酸酐(MAH)单体、丙烯腈(AN)单体作为反应单体，在自由基引发剂的作用下，聚合形成ABS-g-MAH接枝共聚物。本发明生产的ABS-g-MAH具有极低的MAH游离含量以及极高的接枝率，完全满足PC/ABS合金对于ABS-g-MAH相容剂的需求。Aiming at the deficiencies in the prior art, the present invention adopts a high aspect ratio twin-screw extruder as a reactor without adding any solvent, taking styrene-butadiene rubber (SBR) as a matrix polymer, styrene (St) monomer, horse Maic anhydride (MAH) monomers and acrylonitrile (AN) monomers are used as reactive monomers to polymerize to form ABS-g-MAH graft copolymers under the action of free radical initiators. The ABS-g-MAH produced by the invention has extremely low free MAH content and high grafting rate, which fully meets the requirements of PC/ABS alloy for ABS-g-MAH compatibilizer.
本发明是采用以下技术方案实现的：The present invention is realized by adopting the following technical solutions:
一种双螺杆反应挤出马来酸酐接枝改性ABS树脂材料，由以下重量百分数组分组成：A kind of twin-screw reactive extrusion maleic anhydride graft modified ABS resin material is composed of the following components in percentage by weight:
以上组分的重量百分数之和为100％。The sum of the weight percentages of the above components is 100%.
优选的，所述引发剂为自由基引发剂，包括偶氮类引发剂、有机过氧化物类引发剂中至少一种。Preferably, the initiator is a free radical initiator, including at least one of an azo initiator and an organic peroxide initiator.
优选的，所述丁苯橡胶选自苯乙烯含量为20-40wt％的丁苯橡胶。Preferably, the styrene-butadiene rubber is selected from styrene-butadiene rubbers with a styrene content of 20-40 wt%.
本发明还提供了所述双螺杆反应挤出马来酸酐接枝改性ABS组合物的制备方法，包括以下步骤：The present invention also provides the preparation method of described twin-screw reactive extrusion maleic anhydride graft-modified ABS composition, comprising the following steps:
(1)按比例称取丁苯橡胶，通过主喂料加入到双螺杆挤出机中进行搅拌；(1) take styrene-butadiene rubber in proportion, join in twin-screw extruder by main feed and stir;
(2)按比例称取其余组分，混合后得到均一的混合液，再将所述混合液通过液体物料加料口注入双螺杆挤出机中进行反应，在挤出机内高温以及螺纹元件的剪切分散作用下，苯乙烯、丙烯腈、马来酸酐在自由基引发剂的引发作用下发生共聚反应，一部分苯乙烯、丙烯腈、马来酸酐三种单体共聚然后接枝到丁苯橡胶分子链上形成ABS-g-MAH接枝共聚物。(2) Weigh the remaining components in proportion, obtain a uniform mixed solution after mixing, then inject the mixed solution into the twin-screw extruder through the liquid material feeding port to react, and the high temperature and the screw element in the extruder Under the action of shear dispersion, styrene, acrylonitrile, and maleic anhydride undergo copolymerization under the action of a free radical initiator, and a part of the three monomers of styrene, acrylonitrile, and maleic anhydride are copolymerized and then grafted to styrene-butadiene rubber The ABS-g-MAH graft copolymer is formed on the molecular chain.
优选的，步骤(1)所述双螺杆挤出机的螺杆长径比为64:1。Preferably, the screw aspect ratio of the twin-screw extruder described in step (1) is 64:1.
优选的，步骤(2)所述液体物料加料口位于所述双螺杆挤出机螺杆长径比为15:1处。Preferably, the feeding port of the liquid material in step (2) is located at a place where the screw length-to-diameter ratio of the twin-screw extruder is 15:1.
优选的，步骤(2)所述双螺杆挤出机的工艺参数为：Preferably, the process parameters of the twin-screw extruder described in step (2) are:
1区温度170～180℃，2区温度170～180℃，3区温度180～190℃，4区温度190～200℃，模头温度200-210℃，螺杆机转速250r/min。The temperature in zone 1 is 170-180°C, the temperature in zone 2 is 170-180°C, the temperature in zone 3 is 180-190°C, the temperature in zone 4 is 190-200°C, the temperature of the die head is 200-210°C, and the speed of the screw machine is 250r/min.
与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明以双螺杆挤出机为反应容器，通过苯乙烯、丙烯腈以及马来酸酐三种单体之间的共聚物反应形成三元共聚物，然后接枝到丁苯橡胶分子链上，由于苯乙烯/马来酸酐之间的共聚反应竞聚率远远大于1，因此最终产物中几乎不存在游离马来酸酐，相当于最终马来酸酐的接枝率达到了接近100％，因此采用本发明方法可以精确控制ABS-g-MAH接枝共聚物的接枝率，这是传统生产方法无法实现的，具有极大的优势。In the present invention, a twin-screw extruder is used as a reaction vessel to form a terpolymer through the reaction of a copolymer among three monomers of styrene, acrylonitrile and maleic anhydride, and then grafted onto the molecular chain of styrene-butadiene rubber. The reactivity ratio of the copolymerization reaction between styrene/maleic anhydride is far greater than 1, so there is almost no free maleic anhydride in the final product, which is equivalent to the grafting rate of the final maleic anhydride reaching nearly 100%, so this method is adopted The inventive method can accurately control the grafting rate of the ABS-g-MAH graft copolymer, which cannot be realized by traditional production methods, and has great advantages.
具体实施方式detailed description
为使本发明的目的、特征和优点能够更加明显易懂，下面对本发明的具体实施方式做详细的说明。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容更加透彻全面。In order to make the purpose, features and advantages of the present invention more obvious and understandable, the specific implementation manners of the present invention will be described in detail below. However, the present invention can be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that the disclosure of the present invention will be thorough and complete.
实施例1Example 1
(1)称取30公斤丁苯橡胶SBR-1011(台化)，通过主喂料加入长径比为64:1的双螺杆挤出机中进行搅拌塑化，得到丁苯橡胶熔体；(1) Take by weighing 30 kilograms of styrene-butadiene rubber SBR-1011 (Taiwan Chemical), and add the length-to-diameter ratio through the main feed into a twin-screw extruder of 64:1 to carry out stirring and plasticizing to obtain a styrene-butadiene rubber melt;
(2)将0.1公斤自由基引发剂AIBN和0.5公斤马来酸酐单体溶入49.4公斤苯乙烯和20公斤丙烯腈液体中，形成均一的混合液；然后用液体高压柱塞计量泵通过挤出机长径比15:1处液体物料加料口注入双螺杆挤出机中，在双螺杆挤出机螺纹元件的作用下均匀分散于所述丁苯橡胶熔体中；(2) Dissolve 0.1 kg of free radical initiator AIBN and 0.5 kg of maleic anhydride monomer into 49.4 kg of styrene and 20 kg of acrylonitrile liquid to form a uniform mixture; then use a liquid high-pressure plunger metering pump to extrude Inject the liquid material into the twin-screw extruder at the feeding port where the length-to-diameter ratio is 15:1, and evenly disperse in the styrene-butadiene rubber melt under the action of the screw element of the twin-screw extruder;
按比例称取其余组分，混合后得到均一的混合液，再将所述混合液通过液体物料加料口注入双螺杆挤出机中进行反应，在挤出机内高温以及螺纹元件的剪切分散作用下，苯乙烯、丙烯腈、马来酸酐在自由基引发剂的引发作用下发生共聚反应，一部分苯乙烯、丙烯腈、马来酸酐三种单体共聚然后接枝到丁苯橡胶分子链上形成ABS-g-MAH接枝共聚物。在挤出机内高温以及螺纹元件的剪切分散作用下，苯乙烯、丙烯腈、马来酸酐在自由基引发剂的引发作用下发生共聚反应，一部分苯乙烯、丙烯腈、马来酸酐三种单体共聚然后接枝到丁苯橡胶分子链上形成ABS-g-MAH接枝共聚物，进行挤出造粒，最终得到成品材料。其中双螺杆挤出机的工艺参数为：Weigh the remaining components in proportion, mix them to obtain a uniform mixed solution, and then inject the mixed solution into the twin-screw extruder through the liquid material feeding port for reaction. Under the influence of styrene, acrylonitrile, and maleic anhydride, a copolymerization reaction occurs under the action of a free radical initiator, and a part of the three monomers of styrene, acrylonitrile, and maleic anhydride are copolymerized and then grafted onto the molecular chain of styrene-butadiene rubber An ABS-g-MAH graft copolymer is formed. Under the action of high temperature in the extruder and the shear dispersion of threaded components, styrene, acrylonitrile, and maleic anhydride undergo copolymerization reactions under the initiation of free radical initiators, and some of the three types of styrene, acrylonitrile, and maleic anhydride The monomer is copolymerized and then grafted to the molecular chain of styrene-butadiene rubber to form ABS-g-MAH graft copolymer, which is extruded and granulated to finally obtain the finished material. The process parameters of the twin-screw extruder are:
1区温度170～180℃，2区温度170～180℃，3区温度180～190℃，4区温度190～200℃，模头温度200-210℃，螺杆机转速250r/min。The temperature in zone 1 is 170-180°C, the temperature in zone 2 is 170-180°C, the temperature in zone 3 is 180-190°C, the temperature in zone 4 is 190-200°C, the temperature of the die head is 200-210°C, and the speed of the screw machine is 250r/min.
实施例2Example 2
(1)称取32公斤丁苯橡胶SBR-1011(台化)，通过主喂料加入长径比为64:1的双螺杆挤出机中进行搅拌塑化，得到丁苯橡胶熔体；(1) Take by weighing 32 kilograms of styrene-butadiene rubber SBR-1011 (Taiwan Chemical), and add the length-to-diameter ratio through the main feed into the twin-screw extruder of 64:1 to carry out stirring and plasticizing to obtain the styrene-butadiene rubber melt;
(2)将0.2公斤自由基引发剂AIBN和1公斤马来酸酐单体溶入44.8公斤苯乙烯和22公斤丙烯腈液体中，形成均一的混合液；然后用液体高压柱塞计量泵通过挤出机长径比15:1处液体物料加料口注入双螺杆挤出机中，在双螺杆挤出机螺纹元件的作用下均匀分散于所述丁苯橡胶熔体中；(2) Dissolve 0.2 kg of free radical initiator AIBN and 1 kg of maleic anhydride monomer into 44.8 kg of styrene and 22 kg of acrylonitrile liquid to form a uniform mixed solution; then use a liquid high-pressure plunger metering pump to squeeze out Inject the liquid material into the twin-screw extruder at the feeding port where the length-to-diameter ratio is 15:1, and evenly disperse in the styrene-butadiene rubber melt under the action of the screw element of the twin-screw extruder;
按比例称取其余组分，混合后得到均一的混合液，再将所述混合液通过液体物料加料口注入双螺杆挤出机中进行反应，在挤出机内高温以及螺纹元件的剪切分散作用下，苯乙烯、丙烯腈、马来酸酐在自由基引发剂的引发作用下发生共聚反应，一部分苯乙烯、丙烯腈、马来酸酐三种单体共聚然后接枝到丁苯橡胶分子链上形成ABS-g-MAH接枝共聚物。在挤出机内高温以及螺纹元件的剪切分散作用下，苯乙烯、丙烯腈、马来酸酐在自由基引发剂的引发作用下发生共聚反应，一部分苯乙烯、丙烯腈、马来酸酐三种单体共聚然后接枝到丁苯橡胶分子链上形成ABS-g-MAH接枝共聚物，进行挤出造粒，最终得到成品材料。其中双螺杆挤出机的工艺参数为：Weigh the remaining components in proportion, mix them to obtain a uniform mixed solution, and then inject the mixed solution into the twin-screw extruder through the liquid material feeding port for reaction. Under the influence of styrene, acrylonitrile, and maleic anhydride, a copolymerization reaction occurs under the action of a free radical initiator, and a part of the three monomers of styrene, acrylonitrile, and maleic anhydride are copolymerized and then grafted onto the molecular chain of styrene-butadiene rubber An ABS-g-MAH graft copolymer is formed. Under the action of high temperature in the extruder and the shear dispersion of threaded components, styrene, acrylonitrile, and maleic anhydride undergo copolymerization reactions under the initiation of free radical initiators, and some of the three types of styrene, acrylonitrile, and maleic anhydride The monomer is copolymerized and then grafted to the molecular chain of styrene-butadiene rubber to form ABS-g-MAH graft copolymer, which is extruded and granulated to finally obtain the finished material. The process parameters of the twin-screw extruder are:
1区温度170～180℃，2区温度170～180℃，3区温度180～190℃，4区温度190～200℃，模头温度200-210℃，螺杆机转速250r/min。The temperature in zone 1 is 170-180°C, the temperature in zone 2 is 170-180°C, the temperature in zone 3 is 180-190°C, the temperature in zone 4 is 190-200°C, the temperature of the die head is 200-210°C, and the speed of the screw machine is 250r/min.
实施例3Example 3
(1)称取35公斤丁苯橡胶SBR-1011(台化)，通过主喂料加入长径比为64:1的双螺杆挤出机中进行搅拌塑化，得到丁苯橡胶熔体；(1) Take by weighing 35 kilograms of styrene-butadiene rubber SBR-1011 (Taiwan Chemical), and add the length-to-diameter ratio through the main feed into the twin-screw extruder of 64:1 to carry out stirring and plasticizing to obtain the styrene-butadiene rubber melt;
(2)将0.3公斤自由基引发剂AIBN和1.5公斤马来酸酐单体溶入38.2公斤苯乙烯和25公斤丙烯腈液体中，形成均一的混合液；然后用液体高压柱塞计量泵通过挤出机长径比15:1处液体物料加料口注入双螺杆挤出机中，在双螺杆挤出机螺纹元件的作用下均匀分散于所述丁苯橡胶熔体中；(2) Dissolve 0.3 kg of free radical initiator AIBN and 1.5 kg of maleic anhydride monomer into 38.2 kg of styrene and 25 kg of acrylonitrile liquid to form a uniform mixed solution; then use a liquid high-pressure plunger metering pump to squeeze out Inject the liquid material into the twin-screw extruder at the feeding port where the length-to-diameter ratio is 15:1, and evenly disperse in the styrene-butadiene rubber melt under the action of the screw element of the twin-screw extruder;
按比例称取其余组分，混合后得到均一的混合液，再将所述混合液通过液体物料加料口注入双螺杆挤出机中进行反应，在挤出机内高温以及螺纹元件的剪切分散作用下，苯乙烯、丙烯腈、马来酸酐在自由基引发剂的引发作用下发生共聚反应，一部分苯乙烯、丙烯腈、马来酸酐三种单体共聚然后接枝到丁苯橡胶分子链上形成ABS-g-MAH接枝共聚物。在挤出机内高温以及螺纹元件的剪切分散作用下，苯乙烯、丙烯腈、马来酸酐在自由基引发剂的引发作用下发生共聚反应，一部分苯乙烯、丙烯腈、马来酸酐三种单体共聚然后接枝到丁苯橡胶分子链上形成ABS-g-MAH接枝共聚物，进行挤出造粒，最终得到成品材料。其中双螺杆挤出机的工艺参数为：Weigh the remaining components in proportion, mix them to obtain a uniform mixed solution, and then inject the mixed solution into the twin-screw extruder through the liquid material feeding port for reaction. Under the influence of styrene, acrylonitrile, and maleic anhydride, a copolymerization reaction occurs under the action of a free radical initiator, and a part of the three monomers of styrene, acrylonitrile, and maleic anhydride are copolymerized and then grafted onto the molecular chain of styrene-butadiene rubber An ABS-g-MAH graft copolymer is formed. Under the action of high temperature in the extruder and the shear dispersion of threaded components, styrene, acrylonitrile, and maleic anhydride undergo copolymerization reactions under the initiation of free radical initiators, and some of the three types of styrene, acrylonitrile, and maleic anhydride The monomer is copolymerized and then grafted to the molecular chain of styrene-butadiene rubber to form ABS-g-MAH graft copolymer, which is extruded and granulated to finally obtain the finished material. The process parameters of the twin-screw extruder are:
1区温度170～180℃，2区温度170～180℃，3区温度180～190℃，4区温度190～200℃，模头温度200-210℃，螺杆机转速250r/min。The temperature in zone 1 is 170-180°C, the temperature in zone 2 is 170-180°C, the temperature in zone 3 is 180-190°C, the temperature in zone 4 is 190-200°C, the temperature of the die head is 200-210°C, and the speed of the screw machine is 250r/min.
实施例4Example 4
(1)称取37公斤丁苯橡胶SBR-1011(台化)，通过主喂料加入长径比为64:1的双螺杆挤出机中进行搅拌塑化，得到丁苯橡胶熔体；(1) Take by weighing 37 kilograms of styrene-butadiene rubber SBR-1011 (Taiwan Chemical), and add the length-to-diameter ratio through the main feed into the twin-screw extruder of 64:1 to carry out stirring and plasticizing to obtain the styrene-butadiene rubber melt;
(2)将0.2公斤自由基引发剂BPO、0.2公斤自由基引发剂AIBN和2公斤马来酸酐单体溶入33.6公斤苯乙烯和27公斤丙烯腈液体中，形成均一的混合液；然后用液体高压柱塞计量泵通过挤出机长径比15:1处液体物料加料口注入双螺杆挤出机中，在双螺杆挤出机螺纹元件的作用下均匀分散于所述丁苯橡胶熔体中；(2) 0.2 kilograms of free radical initiator BPO, 0.2 kilogram of free radical initiator AIBN and 2 kilograms of maleic anhydride monomers are dissolved in 33.6 kilograms of styrene and 27 kilograms of acrylonitrile liquids to form a uniform mixed solution; The high-pressure plunger metering pump injects the liquid material into the twin-screw extruder through the feeding port of the extruder with a length-to-diameter ratio of 15:1, and is evenly dispersed in the styrene-butadiene rubber melt under the action of the screw elements of the twin-screw extruder ;
按比例称取其余组分，混合后得到均一的混合液，再将所述混合液通过液体物料加料口注入双螺杆挤出机中进行反应，在挤出机内高温以及螺纹元件的剪切分散作用下，苯乙烯、丙烯腈、马来酸酐在自由基引发剂的引发作用下发生共聚反应，一部分苯乙烯、丙烯腈、马来酸酐三种单体共聚然后接枝到丁苯橡胶分子链上形成ABS-g-MAH接枝共聚物。在挤出机内高温以及螺纹元件的剪切分散作用下，苯乙烯、丙烯腈、马来酸酐在自由基引发剂的引发作用下发生共聚反应，一部分苯乙烯、丙烯腈、马来酸酐三种单体共聚然后接枝到丁苯橡胶分子链上形成ABS-g-MAH接枝共聚物，进行挤出造粒，最终得到成品材料。其中双螺杆挤出机的工艺参数为：Weigh the remaining components in proportion, mix them to obtain a uniform mixed solution, and then inject the mixed solution into the twin-screw extruder through the liquid material feeding port for reaction. Under the influence of styrene, acrylonitrile, and maleic anhydride, a copolymerization reaction occurs under the action of a free radical initiator, and a part of the three monomers of styrene, acrylonitrile, and maleic anhydride are copolymerized and then grafted onto the molecular chain of styrene-butadiene rubber An ABS-g-MAH graft copolymer is formed. Under the action of high temperature in the extruder and the shear dispersion of threaded components, styrene, acrylonitrile, and maleic anhydride undergo copolymerization reactions under the initiation of free radical initiators, and some of the three types of styrene, acrylonitrile, and maleic anhydride The monomer is copolymerized and then grafted to the molecular chain of styrene-butadiene rubber to form ABS-g-MAH graft copolymer, which is extruded and granulated to finally obtain the finished material. The process parameters of the twin-screw extruder are:
1区温度170～180℃，2区温度170～180℃，3区温度180～190℃，4区温度190～200℃，模头温度200-210℃，螺杆机转速250r/min。The temperature in zone 1 is 170-180°C, the temperature in zone 2 is 170-180°C, the temperature in zone 3 is 180-190°C, the temperature in zone 4 is 190-200°C, the temperature of the die head is 200-210°C, and the speed of the screw machine is 250r/min.
实施例5Example 5
(1)称取40公斤丁苯橡胶SBR-1011(台化)，通过主喂料加入长径比为64:1的双螺杆挤出机中进行搅拌塑化，得到丁苯橡胶熔体；(1) Take by weighing 40 kilograms of styrene-butadiene rubber SBR-1011 (Taiwan Chemical), add length-to-diameter ratio through the main feeding material and carry out stirring and plasticizing in the twin-screw extruder of 64:1, obtain the styrene-butadiene rubber melt;
(2)将0.25公斤自由基引发剂BPO、0.25公斤自由基引发剂AIBN和3公斤马来酸酐单体溶入26.5公斤苯乙烯和30公斤丙烯腈液体中，形成均一的混合液；然后用液体高压柱塞计量泵通过挤出机长径比15:1处液体物料加料口注入双螺杆挤出机中，在双螺杆挤出机螺纹元件的作用下均匀分散于所述丁苯橡胶熔体中；(2) 0.25 kg of free radical initiator BPO, 0.25 kg of free radical initiator AIBN and 3 kg of maleic anhydride monomer are dissolved in 26.5 kg of styrene and 30 kg of acrylonitrile liquid to form a uniform mixed solution; The high-pressure plunger metering pump injects the liquid material into the twin-screw extruder through the feeding port of the extruder with a length-to-diameter ratio of 15:1, and is evenly dispersed in the styrene-butadiene rubber melt under the action of the screw elements of the twin-screw extruder ;
按比例称取其余组分，混合后得到均一的混合液，再将所述混合液通过液体物料加料口注入双螺杆挤出机中进行反应，在挤出机内高温以及螺纹元件的剪切分散作用下，苯乙烯、丙烯腈、马来酸酐在自由基引发剂的引发作用下发生共聚反应，一部分苯乙烯、丙烯腈、马来酸酐三种单体共聚然后接枝到丁苯橡胶分子链上形成ABS-g-MAH接枝共聚物。在挤出机内高温以及螺纹元件的剪切分散作用下，苯乙烯、丙烯腈、马来酸酐在自由基引发剂的引发作用下发生共聚反应，一部分苯乙烯、丙烯腈、马来酸酐三种单体共聚然后接枝到丁苯橡胶分子链上形成ABS-g-MAH接枝共聚物，进行挤出造粒，最终得到成品材料。其中双螺杆挤出机的工艺参数为：Weigh the remaining components in proportion, mix them to obtain a uniform mixed solution, and then inject the mixed solution into the twin-screw extruder through the liquid material feeding port for reaction. Under the influence of styrene, acrylonitrile, and maleic anhydride, a copolymerization reaction occurs under the action of a free radical initiator, and a part of the three monomers of styrene, acrylonitrile, and maleic anhydride are copolymerized and then grafted onto the molecular chain of styrene-butadiene rubber An ABS-g-MAH graft copolymer is formed. Under the action of high temperature in the extruder and the shear dispersion of threaded components, styrene, acrylonitrile, and maleic anhydride undergo copolymerization reactions under the initiation of free radical initiators, and some of the three types of styrene, acrylonitrile, and maleic anhydride The monomer is copolymerized and then grafted to the molecular chain of styrene-butadiene rubber to form ABS-g-MAH graft copolymer, which is extruded and granulated to finally obtain the finished material. The process parameters of the twin-screw extruder are:
1区温度170～180℃，2区温度170～180℃，3区温度180～190℃，4区温度190～200℃，模头温度200-210℃，螺杆机转速250r/min。The temperature in zone 1 is 170-180°C, the temperature in zone 2 is 170-180°C, the temperature in zone 3 is 180-190°C, the temperature in zone 4 is 190-200°C, the temperature of the die head is 200-210°C, and the speed of the screw machine is 250r/min.
对比例1Comparative example 1
将99.4公斤ABS 750A(台化)、0.5公斤马来酸酐单体、0.1公斤自由基引发剂AIBN混合均匀后通过主喂料加入长径比为64:1的反应型双螺杆挤出机，各段挤出温度如下：99.4 kilograms of ABS 750A (Taiwan Chemical), 0.5 kilograms of maleic anhydride monomer, 0.1 kilogram of free radical initiator AIBN are mixed uniformly and then added into a reactive twin-screw extruder with a length-to-diameter ratio of 64:1 through the main feed, each The segment extrusion temperature is as follows:
1区温度170～180℃，2区温度170～180℃，3区温度180～190℃，4区温度190～200℃，模头温度200-210℃，螺杆机转速250r/min。The temperature in zone 1 is 170-180°C, the temperature in zone 2 is 170-180°C, the temperature in zone 3 is 180-190°C, the temperature in zone 4 is 190-200°C, the temperature of the die head is 200-210°C, and the speed of the screw machine is 250r/min.
在双螺杆挤出机螺纹元件的剪切分散以及引发剂的引发作用下，马来酸酐单体一部分自聚，一部分接枝共聚到ABS分子链上，进行挤出造粒，最终得到成品材料。Under the shear dispersion of the threaded elements of the twin-screw extruder and the initiation of the initiator, a part of the maleic anhydride monomer is self-polymerized, and a part is graft-copolymerized to the ABS molecular chain, extruded and granulated, and finally the finished material is obtained.
对比例2Comparative example 2
将98.8公斤ABS 709(台化)、1公斤马来酸酐单体、0.2公斤自由基引发剂AIBN混合均匀后通过主喂料加入长径比为64:1的反应型双螺杆挤出机，各段挤出温度如下：98.8 kilograms of ABS 709 (Taiwan Chemical), 1 kilogram of maleic anhydride monomer, 0.2 kilogram of free radical initiator AIBN are mixed uniformly and then added into a reactive twin-screw extruder with a length-to-diameter ratio of 64:1 through the main feed, each The segment extrusion temperature is as follows:
1区温度170～180℃，2区温度170～180℃，3区温度180～190℃，4区温度190～200℃，模头温度200-210℃，螺杆机转速250r/min。The temperature in zone 1 is 170-180°C, the temperature in zone 2 is 170-180°C, the temperature in zone 3 is 180-190°C, the temperature in zone 4 is 190-200°C, the temperature of the die head is 200-210°C, and the speed of the screw machine is 250r/min.
在双螺杆挤出机螺纹元件的剪切分散以及引发剂的引发作用下，马来酸酐单体一部分自聚，一部分接枝共聚到ABS分子链上，进行挤出造粒，最终得到成品材料。Under the shear dispersion of the threaded elements of the twin-screw extruder and the initiation of the initiator, a part of the maleic anhydride monomer is self-polymerized, and a part is graft-copolymerized to the ABS molecular chain, extruded and granulated, and finally the finished material is obtained.
对比例3Comparative example 3
将98.2公斤ABS 0215A(台化)、1.5公斤马来酸酐单体、0.3公斤自由基引发剂BPO混合均匀后通过主喂料加入长径比为64:1的反应型双螺杆挤出机，各段挤出温度如下：98.2 kilograms of ABS 0215A (Taiwan Chemical), 1.5 kilograms of maleic anhydride monomer, 0.3 kilograms of free radical initiator BPO are mixed uniformly and then added into a reactive twin-screw extruder with a length-to-diameter ratio of 64:1 through the main feed, each The segment extrusion temperature is as follows:
1区温度170～180℃，2区温度170～180℃，3区温度180～190℃，4区温度190～200℃，模头温度200-210℃，螺杆机转速250r/min。The temperature in zone 1 is 170-180°C, the temperature in zone 2 is 170-180°C, the temperature in zone 3 is 180-190°C, the temperature in zone 4 is 190-200°C, the temperature of the die head is 200-210°C, and the speed of the screw machine is 250r/min.
在双螺杆挤出机螺纹元件的剪切分散以及引发剂的引发作用下，马来酸酐单体一部分自聚，一部分接枝共聚到ABS分子链上，进行挤出造粒，最终得到成品材料。Under the shear dispersion of the threaded elements of the twin-screw extruder and the initiation of the initiator, a part of the maleic anhydride monomer is self-polymerized, and a part is graft-copolymerized to the ABS molecular chain, extruded and granulated, and finally the finished material is obtained.
对比例4Comparative example 4
将97.6公斤ABS 0150(台化)、2公斤马来酸酐单体、0.2公斤自由基引发剂BPO、0.2公斤自由基引发剂AIBN混合均匀后通过主喂料加入长径比为64:1的反应型双螺杆挤出机，各段挤出温度如下：Mix 97.6 kg of ABS 0150 (Taiwan), 2 kg of maleic anhydride monomer, 0.2 kg of free radical initiator BPO, and 0.2 kg of free radical initiator AIBN, and then add the reaction with an aspect ratio of 64:1 through the main feed Type twin-screw extruder, the extrusion temperature of each section is as follows:
1区温度170～180℃，2区温度170～180℃，3区温度180～190℃，4区温度190～200℃，模头温度200-210℃，螺杆机转速250r/min。The temperature in zone 1 is 170-180°C, the temperature in zone 2 is 170-180°C, the temperature in zone 3 is 180-190°C, the temperature in zone 4 is 190-200°C, the temperature of the die head is 200-210°C, and the speed of the screw machine is 250r/min.
在双螺杆挤出机螺纹元件的剪切分散以及引发剂的引发作用下，马来酸酐单体一部分自聚，一部分接枝共聚到ABS分子链上，进行挤出造粒，最终得到成品材料。Under the shear dispersion of the threaded elements of the twin-screw extruder and the initiation of the initiator, a part of the maleic anhydride monomer is self-polymerized, and a part is graft-copolymerized to the ABS molecular chain, extruded and granulated, and finally the finished material is obtained.
对比例5Comparative example 5
将96.5公斤ABS 750N(台化)、3公斤马来酸酐单体、0.25公斤自由基引发剂BPO、0.25公斤自由基引发剂AIBN混合均匀后通过主喂料加入长径比为64:1的反应型双螺杆挤出机，各段挤出温度控制如下：Mix 96.5 kg of ABS 750N (Taiwan), 3 kg of maleic anhydride monomer, 0.25 kg of free radical initiator BPO, and 0.25 kg of free radical initiator AIBN, and then add the reaction with an aspect ratio of 64:1 through the main feed Type twin-screw extruder, the extrusion temperature of each section is controlled as follows:
1区温度170～180℃，2区温度170～180℃，3区温度180～190℃，4区温度190～200℃，模头温度200-210℃，螺杆机转速250r/min。The temperature in zone 1 is 170-180°C, the temperature in zone 2 is 170-180°C, the temperature in zone 3 is 180-190°C, the temperature in zone 4 is 190-200°C, the temperature of the die head is 200-210°C, and the speed of the screw machine is 250r/min.
在双螺杆挤出机螺纹元件的剪切分散以及引发剂的引发作用下，马来酸酐单体一部分自聚，一部分接枝共聚到ABS分子链上，进行挤出造粒，最终得到成品材料。Under the shear dispersion of the threaded elements of the twin-screw extruder and the initiation of the initiator, a part of the maleic anhydride monomer is self-polymerized, and a part is graft-copolymerized to the ABS molecular chain, extruded and granulated, and finally the finished material is obtained.
将对比例1-5和实施例1-5共计10种材料通过索氏抽提器将马来酸酐游离残单去除后，采用滴定法测试马来酸酐最终接枝率，详细见表1。After a total of 10 kinds of materials in Comparative Examples 1-5 and Examples 1-5 were removed by Soxhlet extractor, the maleic anhydride free residues were removed, and the final grafting rate of maleic anhydride was tested by titration method, as shown in Table 1 for details.
表1对比例和实施例材料的马来酸酐接枝率The maleic anhydride graft ratio of table 1 comparative example and embodiment material
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only express several implementation modes of the present invention, and the descriptions thereof are relatively specific and detailed, but should not be construed as limiting the patent scope of the present invention. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention should be based on the appended claims.
Claims (7)
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| CN101967216A (en) * | 2010-09-29 | 2011-02-09 | 深圳市科聚新材料有限公司 | Maleic anhydride melt-grafted ABS and preparation method thereof |
| CN105778319A (en) * | 2014-12-23 | 2016-07-20 | 上海华谊聚合物有限公司 | High-acrylonitrile-content ABS and preparation method thereof |
| CN115103865A (en) * | 2019-12-17 | 2022-09-23 | 英力士苯领集团股份公司 | Styrene/acrylonitrile dual-initiator grafting polybutadiene latex technology |
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| US4692498A (en) * | 1983-09-26 | 1987-09-08 | The Standard Oil Company | Novel rubber-modified thermoplastic resin compositions |
| CN101967216A (en) * | 2010-09-29 | 2011-02-09 | 深圳市科聚新材料有限公司 | Maleic anhydride melt-grafted ABS and preparation method thereof |
| CN105778319A (en) * | 2014-12-23 | 2016-07-20 | 上海华谊聚合物有限公司 | High-acrylonitrile-content ABS and preparation method thereof |
| CN115103865A (en) * | 2019-12-17 | 2022-09-23 | 英力士苯领集团股份公司 | Styrene/acrylonitrile dual-initiator grafting polybutadiene latex technology |
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