CN1115355C - 制备橡胶基材的方法 - Google Patents
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- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
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Classifications
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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
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/18—Increasing the size of the dispersed particles
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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
- C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
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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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/902—Core-shell
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/942—Polymer derived from nitrile, conjugated diene and aromatic co-monomers
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
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Abstract
本发明公开了一种制备橡胶基材的方法。在该方法中，首先聚合50-95重量份共轭二烯单体，直到生成的第一橡胶基材的凝胶含量为5-70%重量。之后，第一橡胶基材与5-50重量份单体二次聚合，以得到第二橡胶基材。所得的第二橡胶基材中芯的凝胶含量高于外层的凝胶含量。
Description
技术领域
本申请是基于1998.3.20日在韩国工业产权局提交的No.98-9632申请，该申请的内容在本文引为参考。
本发明涉及制备橡胶基材的方法，更具体地，本发明涉及橡胶基材的制备方法，该橡胶基材能制备具有大粒径且橡胶粒径分布窄的橡胶胶乳。
背景技术
接枝聚合物如ABS(丙烯腈-丁二烯-苯乙烯)在橡胶工业是公知的，其制备方法以及其在各种领域中的应用的优点也是公知的。通常，ABS接枝聚合物(树脂)含有由共轭二烯如丁二烯形成的橡胶基材或主链部分，和接枝部分。
ABS的耐冲击性受橡胶基材颗粒的粒径和分布的影响。为了增加ABS树脂的耐冲击性，应提高用于制备ABS树脂的橡胶基材颗粒的粒径。
为了增加粒径，把橡胶基材颗粒与酸性材料如乙酸或磷酸接触，并降低该颗粒的pH值及凝固这些颗粒。由于颗粒彼此凝固从而增加了粒径。在本申请中，橡胶基材指凝固前具有小粒径的橡胶胶乳，橡胶胶乳指凝固后具有大粒径的橡胶胶乳。上述方法公开在日本专利特公召sho 63-132903、Sho 63-117005、Hei 7-157501，和日本专利Hei 2-9601、Sho55-19246和Sho 42-3112中。
由上述方法制得的橡胶胶乳颗粒的粒径与分布受酸性材料的含量及橡胶基材颗粒的凝胶含量的影响。如果凝胶含量较高，则减少了橡胶乳中不想要的凝块，但粒径较小且粒径分布宽，降低了橡胶胶乳的耐冲击性。如果凝胶含量较小，橡胶胶乳的粒径大且粒径分布窄，但出现过量的凝块。
另外，凝胶含量显著依赖于反应速率。因此，当反应速率提高时，凝胶含量增加，有大量待反应的胶乳颗粒。由于这些原因，在凝固过程中通过加入酸性材料不可能增加粒径且使粒径分布变窄。
发明内容
本发明的一个目的在于提供一种制备橡胶基材的方法，该橡胶基材包括一个芯和其凝胶含量不同的外层。
本发明另外一个目的在于提供一种具有大粒径且窄粒径分布的橡胶基材的制备方法。
为了完成这些和其它目的，该制备橡胶基材的方法包括下列步骤：首先聚合50-95重量份脂族共轭二烯单体(基于100重量份总单体)，直到首先聚合的产物的凝胶含量为5-70％。
另外，该方法包括步骤：第二次聚合首先聚合的产物与5-50重量份的单体，基于100重量份总单体。
由本发明的方法制得的橡胶基材具有一个芯和在该芯上形成的外层。芯的凝胶含量高于外层的凝胶含量。使用该橡胶基材，可得到大粒径且窄粒径分布的橡胶胶乳。另外，当使用所得的橡胶胶乳制备ABS树脂时，可得到具有优良耐冲击性的ABS树脂。
具体实施方式
首先乳液聚合50-95重量份单体，以100重量份的总单体计。乳液聚合法在本领域中是公知的，并在乳液聚合介质中通常包括洗涤剂(表面活性剂)，引发剂和分子量调节剂。
单体可仅是脂族共轭二烯单体或是共轭二烯单体与可共聚的烯属不饱和单体的混合物。共轭二烯单体可以是1，3-丁二烯、异戊二烯、氯丁二烯和其共聚单体。该可共聚单体可以是脂族乙烯化合物，如苯乙烯，α-甲基苯乙烯和丙烯腈化合物，如丙烯腈。在混合单体中，可共聚单体少于20重量份。
洗涤剂可以是烷基芳基磺酸酯、碱金属硫酸盐、磺化的烷基酯、脂肪酸皂、松香酸的碱性盐(如松脂酸钾)、油酸的碱性盐(如油酸钾)和其混合物。洗涤剂的存在量可为1-4重量份。
引发剂可以是水溶性过硫酸盐式过氧化合物和水溶性氧化还原引发系统。过硫酸盐可是过硫酸钠或钾。油溶性引发剂可以是氢过氧化枯烯、氢过氧化二异丙苯、偶氮二异丁基腈、氢过氧化叔丁基、氢过氧化对甲烷、过氧化苯甲酰(benzoly perozide)和其混合物。另外，可使用水溶和脂溶自由基引发剂的混合物。引发剂的量为0.1-0.6重量份。
乳液聚合介质可以是KCl、NaCl、KHCO3、NaHCO3、K2CO3、Na2CO3、KHSO3、NaHSO3、K4P2O7、Na4P2O7、K3PO4、Na3PO4、K2HPO4、Na2HPO4和其混合物。介质的量可以是0.2-1重量份。分子量调节剂可以是正辛基硫醇、环己基硫醇、双戊烯二硫醇，己丁基硫醇，正十二烷硫醇，叔十二烷基硫醇。分子量调节剂存在量为0.1-0.5重量份。
首次乳液聚合是在50-70℃下进行约5-15小时。首次乳液聚合后，该橡胶基材芯的凝胶含量为5-70％重量。
之后，该橡胶基材芯与5-50重量份单体、0.05-1.2重量份分子量调节剂反应，制得在该橡胶基材芯上的外层。
芯的凝胶含量高于外层的凝胶含量。该橡胶基材的平均粒径为700-1500埃，粒径分布小于25％。另外，该橡胶基材的凝胶含量为70-99％，凝胶的溶胀指数为16-40。
当这种橡胶基材用于制备橡胶胶乳时，可制得具有大粒径、窄粒径分布的橡胶胶乳。关于橡胶胶乳的制备方法，可使用常规方法，包括将橡胶基材与酸性材料如乙酸接触。当橡胶胶乳具有大粒径、窄粒径分布时，可使用该橡胶胶乳制备具有优良耐冲击性的ABS树脂。
参照下列实施例，更详细地介绍本发明。本发明可用各种方式加以实施，且不受这些实施例的限制。
橡胶基材的制备
实施例1a1)首次聚合
向装有氮气的聚合反应器(高压釜)中，一次性加入110重量份去离子水，85重量份1，3-丁二烯、1，2重量份松脂酸钾、1∶5重量份油酸钾、0.1重量份Na2CO3、0.5重量份KHCO3、0.3重量份叔十二烷基硫醇和0.3重量份过硫酸钾，并聚合，得到橡胶基材的芯。该反应在55℃下进行10小时。2)二次聚合
向该反应器中一次性加入15重量份1，3-丁二烯和0.05叔十二烷基硫醇，并在65℃下与该橡胶基材芯反应8小时。
实施例2a-4a和比较例1a-2a。
以与实施例1a相同的方法制备橡胶基材，除了改变组合物的量，加入方法和首次聚合时间外，如下表1所示。
用下列测试方法测定实施例1a-4a和比较例1a-2a的橡胶基材的转化率、凝胶含量、溶胀系数粒径和生成的凝块。结果列于表1中。表1中，“EX”指实施例，“COM”指比较例。1)凝胶含量和溶胀指数
实施例1a的橡胶基材用稀酸凝固、洗涤并60℃下在烘箱中真空干燥24小时。用剪刀把干燥的橡胶切成薄片。把1g薄橡胶基材加入到100g甲苯中，并在室温下暗室中存放48小时。48小时后，该薄橡胶基材分成溶胶和凝胶。使用实施例2a-4a和比较例1a-2a的橡胶基材进行同样的测试。
用下列公式1和2，计算凝胶含量和溶胀指数。公式1凝胶含量(％)＝[未溶解材料(凝胶)的重量/样品的重量]×100公式2溶胀指数＝溶胀凝胶的重量/总凝胶的重量2)粒径和其分布
用Nicomp 370 HPL使用动态激光扫描法测定粒径和其分布。3)凝固材料的百分数
用公式3计算凝固材料的百分数。公式3凝固材料的百分数＝[在反应器中制得的凝固材料的重量/所加的总单体的重量]×1004)接枝聚合物的百分数
用公式4计算接枝聚合物的百分数公式4接枝聚合物的百分数＝[接枝单体的重量/橡胶基材的重量]×100
表1
| EX1a | EX2a | EX3a | EX4a | COM1a | COM2a | |
| 去离子水 | 110 | 115 | 100 | 110 | 115 | 112 |
| 1，3-丁二烯 | 85 | 70 | 55 | 90 | 100 | 45 |
| 松脂酸钾 | 1.2 | 1.3 | 1 | 1.1 | 1.3 | 1.1 |
| 油酸钾 | 1.5 | 1.4 | 1.6 | 1.6 | 1.4 | 1.6 |
| 碳酸钠 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| 碳酸氢钾 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| 叔十二烷基硫醇 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| 过硫酸钾 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| 二次聚合前的凝胶含量 | 50％ | 10％ | 10％ | 30％ | 200％ | |
| 加入方法 | 一次性 | 一次性 | 一次性 | 连续 | 一次性 | |
| 首次聚合时间 | 11小时 | 7小时 | 9小时 | 10小时 | 6小时 | |
| 1，3-丁二烯 | 15 | 30 | 45 | 10 | 55 | |
| 叔十二烷基硫醇 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | |
| 单体的聚合物转化率 | 92％ | 90％ | 90％ | 90％ | 90％ | 90％ |
| 凝胶含量 | 90％ | 75％ | 83％ | 85％ | 88％ | 65％ |
| 溶胀指数 | 18 | 24 | 21 | 20 | 19 | 26 |
| 粒径 | 900埃 | 1000埃 | 800埃 | 850埃 | 900埃 | 1300埃 |
| 不想要的凝块的量 | 低于0.15％ | 低于0.10％ | 低于0.10％ | 低于0.10％ | 0.50％ | 0.50％ |
如表1所示，所得的不想要的凝块的量少于比较例的量。
橡胶胶乳的制备
实施例1b
把100重量份实施例1a的橡胶基材加入到反应器中。搅拌速度和温度分别控制在30rpm和30℃。向该反应器在1小时内缓慢加入3.5重量份7％的乙酸水溶液。之后，停止搅拌，并静置所得的产物30分钟，以制得橡胶胶乳。
实施例2b和4b和比较例1b和2b
以制备实施例1b相同的方法制备橡胶胶乳，除了使用实施例2a和4a，比较例1a和2a所得的橡胶基材外。
在实施例1b、2b和4b、及比较例1b和2b中所得的橡胶颗粒的粒径、粒径分布和胶乳的pH的结果列于表2。
表2
| EX1b | EX2b | EX4b | COM1b | COM2b | |
| 粒径 | 3300埃 | 3200埃 | 3350埃 | 2900埃 | 2800埃 |
| 粒径分布 | 10％ | 8％ | 20％ | 35％ | 30％ |
| 胶乳的pH | 10.5 | 10.6 | 10.4 | 10.5 | 10.5 |
如表2所示，实施例1b、2b和4b的粒径大于比较例1b和2b的粒径。另外，实施例1b、2b和4b的分布比比较例1b和2b的窄。
ABS树脂的制备
实施例1c
向反应器中一次性加入实施例1b中制得的50重量份橡胶胶乳、65重量份去离子水、0.1重量份四乙酸亚甲基二胺钠、0.05重量份硫酸铁、0.23重量份甲醛化次硫酸钠和0.35重量份松脂酸钾。反应器的温度升高到70℃。之后，在3小时内把混合的乳液连续地加到该反应器中，并把温度升到80℃。该混合乳液通过如下方式制备：混合50重量份去离子水、0.65重量份松脂酸钾、35重量份苯乙烯、15重量份丙烯腈、0.4重量份叔十二烷基硫醇和0.4重量份氢过氧化二异丙苯。
把该混合物静置1小时，并终止该反应。生成的聚合物从单体到聚合物的转化率为98％，接枝聚合物的百分数为30％，凝块的百分数为0.3％。
实施例2c和比较例1c和2c。
使用与实施例1b相同的方法制备ABS树脂，除了使用实施例2b和比较例1b和2b中制得的橡胶胶乳外。
由实施例1c和2c及比较例1c和2c制得的ABS树脂分别用硫酸水溶液凝固来得到粉末。把36重量份粉末和64重量份SAN(由LG ChemicalsCo.Ltd.生产和销售，商标名为80HF)加入到混合器中并混合。该混合物用挤塑机成粒并注塑。测定所得产物的冲击强度和挠曲强度，其结果列于表3。
表3
| EX1c | EX2c | COM1c | COM2c | ||
| 缺口伊佑德冲击强度(ASTM D256，kg·cm/cm) | (23℃) | 42 | 40 | 36 | 35 |
| (-20℃) | 22 | 21 | 16 | 15 | |
| 挠曲强度(ASTM D12 38，g/10分，10kg，220℃) | 16 | 16 | 15 | 15 | |
如表3所示，用实施例1b和2b制得的ABS树脂具有优良的耐冲击性。
Claims (5)
1.一种制备橡胶基材的方法，包括下列步骤：
首先聚合50-95重量％脂族共轭二烯单体或脂族共轭二烯单体和与其可共聚的烯属不饱单体的混合物来形成橡胶基材的芯，直到橡胶基材芯的凝胶含量为5-70％重量；和
二次聚合橡胶基材芯和5-50重量％该脂族共轭二烯单体或该混合物，以在橡胶基材芯上形成外层，并进一步聚合该芯。
2.权利要求1的方法，其中二次聚合后得到的橡胶基材的平均粒径为700-1500埃。
3.权利要求1的方法，其中二次聚合后得到的橡胶基材的凝胶含量为70-99％重量，溶胀指数为16-40。
4.权利要求1的方法，其中脂族共轭二烯单体是至少选自1，3-丁二烯，异戊二烯和氯丁二烯的一种。
5.权利要求1的方法，其中可共聚单体选自芳族乙烯基化合物、丙烯酸酯、甲基丙烯酸酯和丙烯腈化合物。
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| KR100548626B1 (ko) * | 2003-10-29 | 2006-01-31 | 주식회사 엘지화학 | 고무라텍스 및 이의 제조방법 |
| KR101638240B1 (ko) * | 2013-09-30 | 2016-07-08 | 주식회사 엘지화학 | 고무질 중합체, 그라프트 공중합체와 이들의 제조방법, 내충격 내열수지 조성물 |
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| US4877844A (en) * | 1985-05-10 | 1989-10-31 | Mitsubishi Rayon Company Limited | Process for producing a low gloss thermoplastic resin |
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| US5719232A (en) * | 1994-04-22 | 1998-02-17 | Bayer Aktiengesellschaft | ABS type thermoplastic moulding compounds |
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| US4243765A (en) * | 1976-12-29 | 1981-01-06 | The Dow Chemical Company | Impact-resistant polymers and rubber concentrates therefor |
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| US4336355A (en) * | 1980-10-20 | 1982-06-22 | Monsanto Company | Process for grafting large rubber particles as ABS polyblends |
| MX168323B (es) * | 1986-10-21 | 1993-05-18 | Rohm & Haas | Modificadores de impacto de nucleo cubierto para resinas estirenicas |
| JPH0721014B2 (ja) * | 1986-11-26 | 1995-03-08 | 宇部サイコン株式会社 | ポリマ−ラテツクスの連続凝集方法 |
| JPH0721012B2 (ja) * | 1986-11-04 | 1995-03-08 | 宇部サイコン株式会社 | ポリマーラテックスの凝集方法 |
| JPH029601A (ja) | 1988-06-28 | 1990-01-12 | Dantani Plywood Co Ltd | 集成材とその製造方法 |
| JPH0517507A (ja) * | 1991-07-16 | 1993-01-26 | Asahi Chem Ind Co Ltd | 共重合体ラテツクスの製造法 |
| JPH06119796A (ja) * | 1992-10-06 | 1994-04-28 | Texas Instr Japan Ltd | 欠陥メモリセル救済用デコーダ |
| JP3275979B2 (ja) | 1993-12-09 | 2002-04-22 | 日本エイアンドエル株式会社 | ジエン系重合体ラテックスの肥大化方法 |
| KR100380014B1 (ko) * | 1998-03-20 | 2003-08-19 | 주식회사 엘지화학 | 고무질 중합체 라텍스 제조 방법 |
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| US4877844A (en) * | 1985-05-10 | 1989-10-31 | Mitsubishi Rayon Company Limited | Process for producing a low gloss thermoplastic resin |
| CN1087646A (zh) * | 1992-12-03 | 1994-06-08 | 瓦克化学有限公司 | 一种制备改进核壳间相结合的核-壳分散粒子型接枝共聚物胶乳的方法 |
| US5719232A (en) * | 1994-04-22 | 1998-02-17 | Bayer Aktiengesellschaft | ABS type thermoplastic moulding compounds |
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