WO2005105909A1 - Stabilisant thermique composite a base d'hydrotalcite pour un haut polymere contenant du chlore - Google Patents

Stabilisant thermique composite a base d'hydrotalcite pour un haut polymere contenant du chlore Download PDF

Info

Publication number
WO2005105909A1
WO2005105909A1 PCT/CN2004/001113 CN2004001113W WO2005105909A1 WO 2005105909 A1 WO2005105909 A1 WO 2005105909A1 CN 2004001113 W CN2004001113 W CN 2004001113W WO 2005105909 A1 WO2005105909 A1 WO 2005105909A1
Authority
WO
WIPO (PCT)
Prior art keywords
zinc
chlorine
hydrotalcite
soap
calcium
Prior art date
Application number
PCT/CN2004/001113
Other languages
English (en)
Chinese (zh)
Inventor
Xue Duan
Dianqing Li
Yanjun Lin
Original Assignee
Beijing University Of Chemical Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Beijing University Of Chemical Technology filed Critical Beijing University Of Chemical Technology
Publication of WO2005105909A1 publication Critical patent/WO2005105909A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids

Definitions

  • the present invention relates to a hydrotalcite-based chlorine-containing polymer composite thermal stabilizer, and particularly to a calcium / zinc compound-containing hydrotalcite-based chlorine-containing polymer composite thermal stabilizer. Background technique
  • PVC resin has the characteristics of difficult to burn, high mechanical properties, low price, rich raw material source, mature manufacturing process, etc. It is widely used in construction, telecommunications, transportation, electronics, chemical industry, packaging and other industries. Two major types of general-purpose thermoplastics. However, the thermal stability of PVC itself is very poor. Its flow temperature is 136 ° C and its decomposition temperature is 140 ° C. The difference between the two is only 4 ° C, which brings great difficulties to processing and use. Therefore, a certain amount of heat must be added. stabilizer. Other chlorine-containing polymers also undergo autocatalytic reactions to de-HC1 under heat or ultraviolet radiation, reducing various properties of the material.
  • Heat stabilizers are one of the essential wife additives for the processing of PVC and other chlorine-containing polymers.
  • thermal stabilizers can be mainly divided into basic lead salts, metal soaps, organic tins, rare earths and composite stabilizers according to their chemical structure.
  • PVC heat stabilizers With the strengthening of environmental protection awareness, PVC heat stabilizers are developing in the direction of low toxicity, pollution-free and high efficiency. It is of great significance to research and develop a new generation of green and environmentally friendly PVC heat stabilizers.
  • Hydrotalcite also known as Layered Double Hydroxides (LDHs)
  • LDHs Layered Double Hydroxides
  • the surface of the laminate is alkaline, it can absorb the aci released from the pyrolysis of PVC and other chlorine-containing polymers, thereby inhibiting its autocatalytic decomposition.
  • thermal stability mechanism is due to LDHs.
  • the exchangeability of interlayer ions allows interlayer C0 3 2 to exchange with HC1 entering the interlayer, so as to absorb HC1, stabilize PVC and other chlorine-containing polymers.
  • Hydrotalcite-filled PVC is compounded with other thermal stabilizers, such as organic, lead, or zinc salts, to further improve the thermal stability of PVC.
  • the heat stability time of PVC can be extended to 62 minutes at 180 ° C. Under the same conditions, using 2 parts of stearic acid / zinc stearate thermal stabilizer, the thermal stabilization time is only 38 minutes.
  • hydrotalcite is compounded with other thermal stabilizers, which overcomes the shortcomings of using hydrotalcite as a thermal stabilizer alone, which has poor initial colorability.
  • thermal stabilizers which overcomes the shortcomings of using hydrotalcite as a thermal stabilizer alone, which has poor initial colorability.
  • most of them use toxic elements such as lead and tin, which is not conducive to the development of hydrotalcite completely replacing the existing expensive or toxic thermal stabilizers. Summary of the invention
  • the purpose of the present invention is to overcome the shortcomings of the existing hydrotalcite-based chlorine-containing polymer composite heat stabilizers containing toxic elements such as lead and tin, and provide a hydrotalcite-based chlorine-containing polymer composite heat that does not contain toxic elements. stabilizer.
  • the chlorine-containing polymer heat stabilizer provided by the present invention is a mixture, and its components and contents are: hydrotalcite: 10-82%
  • Zinc soap 1-47%
  • the more preferred ratio is:
  • the above percentages are all mass 3 ⁇ 4 ⁇ fractions.
  • the three components are thoroughly mixed to obtain a chlorine-containing polymer composite thermal stabilizer.
  • the calcium soap used in the present invention is one of calcium stearate, calcium octoate, calcium laurate, calcium palmitate, calcium oleate, calcium benzoate, and maleic acid, preferably stearic acid and lauric acid. Calcium and calcium benzoate.
  • the zinc soap used in the present invention is one of zinc stearate, zinc caprylate, zinc laurate, zinc palmitate, catalole oleate, zinc benzoate, and zinc maleate.
  • Zinc stearate and zinc laurate are preferred.
  • zinc benzoate is preferred.
  • the hydrotalcite used in the present invention is a magnesium-aluminum hydrotalcite whose interlayer anion is carbonate, in which the molar ratio of Mg 2+ / Al 3+ satisfies a ratio of 2-4: 1. Its composition should satisfy the following general formula: [Mg 2 V x Al 3+ x (OH) 2 ] C0 3 2 " x / 2 -mH 2 0, where 0.2 ⁇ x ⁇ 0.33; (Km 2. This hydrotalcite is best It is surface modified by organics, which is good for it in polymers ⁇ :.
  • the hydrotalcite used in the present invention can adopt a variable pH method (also known as a single drop method or a high supersaturation method), a constant pH method (also known as a double drop method or a low supersaturation method), and nucleation / crystallization Co-precipitation methods such as isolation method and urea method, or can be prepared by methods such as hydrothermal synthesis method and roasting reduction method.
  • a variable pH method also known as a single drop method or a high supersaturation method
  • a constant pH method also known as a double drop method or a low supersaturation method
  • nucleation / crystallization Co-precipitation methods such as isolation method and urea method
  • n (OH—) / [n (Mg 2+ ) + n (Al 3+ )] 1.4
  • the ratio of -2.2 is formulated into a mixed solution, which has the same volume as the mixed salt solution.
  • the soluble carbonate may be any of Na 2 C0 3 , K 2 C0 3 , and (M 4 ) 2 C0 3 .
  • the two solutions are rapidly mixed in a rotating liquid film reactor, and the slurry obtained after mixing is crystallized under reflux at 100 ° C for 6-10 hours, the precipitate is washed to pH «7, and filtered to obtain a hydrotalcite filter cake, and dried water The talc filter cake gives hydrotalcite powder.
  • hydrotalcite powder If you want to obtain surface-modified hydrotalcite powder, add the washed and filtered filter-cake to about 23-35 times the solid content of the filter cake, heat up to 80-100 ° C, and add 4-7% solid content The stearic acid was stirred and reacted for 2-5 hours. After drying, an organic hydrotalcite powder was obtained on the surface. Prepared by the method of particle size distribution of the hydrotalcite is 2 0nm- 120nm.
  • the composite heat stabilizer provided by the present invention is mainly used in chlorine-containing polymers, usually polyvinyl chloride, chlorinated polyethylene, chlorinated polyvinyl chloride, vinyl chloride-ethylene copolymer, vinyl chloride-acid copolymerization. Things.
  • the amount of the heat stabilizer (based on parts by mass) is preferably 0.1 to 10 parts in 100 parts of the chlorine-containing polymer, and the preferred amount is 3 to 6 parts. ⁇
  • the static thermal aging experiment was performed on polyvinyl chloride and chlorinated polyethylene (CPE) added with the composite thermal stabilizer, and the results show that the composite thermal stabilizer provided by the present invention can effectively improve PVC and other chlorine-containing polymers.
  • Thermal stability Under the environment of 180 ⁇ 1 ° C, PVC and chlorine-containing polymers show good initial colorability, and the heat stability time can reach more than 80-220 minutes. PVC and chlorine-containing polymers without adding heat stabilizers Its thermal stability time is only 6-10 minutes. detailed description
  • the slurry obtained after mixing is crystallized at reflux for 6 h at 100 ° C.
  • the precipitate is washed to pH «7 to obtain a hydrotalcite filter cake.
  • a hydrotalcite powder with a surface-modified magnesium / aluminum ratio of 2 can be obtained.
  • the amount of MgS0 4 and A1 2 (S0 4 ) 3 ⁇ 18H 2 0 is changed so that the molar ratio of Mg 2+ / Al 3+ in the mixed solution is 2.5, 3, 3.5, and 4 to obtain magnesium / aluminum.
  • hydrotalcite was mixed with 4-stearic acid and zinc stearate in the proportions of 30%, 60%, and 10%, respectively, to obtain a chlorine-containing polymer composite thermal stabilizer.
  • DOP diisooctyl phthalate
  • SSR-Z4 plastic experimental machine at 14CTC for 10 minutes.
  • a sheet with a thickness of 1 cm was pressed and cut into 1 cm X 1 cm test pieces.
  • the test piece was placed in a thermal aging test box at 180 ° C and 1 ° C for static aging experiments. The time when the test piece started and the black decomposition point appeared as the thermal stabilization time.
  • Table 1 The results are shown in Table 1:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un stabilisant thermique composite à base d'hydrotalcite pour un haut polymère contenant du chlore. Ce stabilisant thermique est constitué d'hydrotalcite, de savon de calcium et de savon de zinc, dans des proportions définies. L'ingrédient principal de ce stabilisant thermique composite est [Mg2+1-xAl3+x(OH)2]CO32-x/2 . mH2O (0,2≤x≤0,33; 0≤m≤2). Le stabilisant thermique composite selon cette invention confère une meilleure stabilité thermique au PVC et autre polymère supérieur contenant du chlore, il n'est pas toxique, ne pollue pas, est économique, sa matière première est abondante, etc.
PCT/CN2004/001113 2004-04-29 2004-09-28 Stabilisant thermique composite a base d'hydrotalcite pour un haut polymere contenant du chlore WO2005105909A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN 200410037656 CN1252159C (zh) 2004-04-29 2004-04-29 一种水滑石基pvc复合热稳定剂
CN200410037656.7 2004-04-29

Publications (1)

Publication Number Publication Date
WO2005105909A1 true WO2005105909A1 (fr) 2005-11-10

Family

ID=34601511

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2004/001113 WO2005105909A1 (fr) 2004-04-29 2004-09-28 Stabilisant thermique composite a base d'hydrotalcite pour un haut polymere contenant du chlore

Country Status (2)

Country Link
CN (1) CN1252159C (fr)
WO (1) WO2005105909A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112694699A (zh) * 2020-12-22 2021-04-23 深圳市信维通信股份有限公司 一种含氟聚合物的应用及其制备方法

Families Citing this family (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100457807C (zh) * 2005-03-28 2009-02-04 同济大学 一种Mg-A1水滑石热稳定剂及其制备方法
CN100448927C (zh) * 2006-12-22 2009-01-07 郴州浩伦生化助剂有限公司 用于聚氯乙烯的无毒片状热稳定剂及制备工艺
CN101774548B (zh) * 2010-03-15 2011-04-27 北京泰克来尔科技有限公司 共沉淀法制备层状复合金属氢氧化物的母液重复利用技术
CN101967253A (zh) * 2010-10-26 2011-02-09 湘乡市贝特尔塑胶有限公司 一种环保型pvc钙锌复合稳定剂
CN102070858B (zh) * 2010-12-22 2012-02-01 西南大学 Pvc用钠锌复合稳定剂及其制备方法
CN102070857B (zh) * 2010-12-22 2012-02-01 西南大学 Pvc用钙锌复合稳定剂及其制备方法
CN102304257B (zh) * 2011-08-25 2013-03-06 上海恒方大高分子材料科技有限公司 一种适用蒸汽灭菌的医用pvc材料及其制备方法
CN102796281B (zh) * 2012-08-16 2015-01-14 广东生益科技股份有限公司 用于溴化改性环氧覆铜板的耐热性填料及用于覆铜板的溴化环氧树脂组合物
CN104893136A (zh) * 2014-03-03 2015-09-09 南通艾德旺化工有限公司 一种改性复合镁铝水滑石热稳定剂的制备方法
CN104277368B (zh) * 2014-09-17 2016-08-31 湖南稀土金属材料研究院 稀土类水滑石复合热稳定剂及热稳定聚氯乙烯
CN104710649A (zh) * 2015-03-24 2015-06-17 宁波高新区零零七工业设计有限公司 一种水滑石热稳定剂的制备方法
CN105295246A (zh) * 2015-11-18 2016-02-03 安徽华塑股份有限公司 一种pvc用水滑石氰尿酸镧复合环保稳定剂及其制备方法
CN105295242A (zh) * 2015-11-18 2016-02-03 安徽华塑股份有限公司 一种pvc用水滑石复合环保稳定剂及其制备方法
CN105295245A (zh) * 2015-11-18 2016-02-03 安徽华塑股份有限公司 一种pvc用水滑石戊二酸锌复合环保稳定剂及其制备方法
CN105295243A (zh) * 2015-11-18 2016-02-03 安徽华塑股份有限公司 一种pvc用水滑石油酸稀土复合环保稳定剂及其制备方法
CN105419146A (zh) * 2015-11-18 2016-03-23 安徽华塑股份有限公司 一种pvc用水滑石月桂酸镧复合环保稳定剂及其制备方法
CN105295248A (zh) * 2015-11-18 2016-02-03 安徽华塑股份有限公司 一种pvc用水滑石二聚酸镧复合环保稳定剂及其制备方法
CN105295244A (zh) * 2015-11-18 2016-02-03 安徽华塑股份有限公司 一种pvc用水滑石有机锡复合环保稳定剂及其制备方法
CN105295249A (zh) * 2015-11-18 2016-02-03 安徽华塑股份有限公司 一种pvc用水滑石稀土复合环保稳定剂及其制备方法
CN105295218A (zh) * 2015-11-18 2016-02-03 安徽华塑股份有限公司 一种pvc用水滑石蓖麻油酸镧复合环保稳定剂及其制备方法
CN105255064A (zh) * 2015-11-18 2016-01-20 安徽华塑股份有限公司 一种pvc用水滑石柠檬酸稀土复合环保稳定剂及其制备方法
CN105295247A (zh) * 2015-11-18 2016-02-03 安徽华塑股份有限公司 一种pvc用水滑石硬脂酸镧复合环保稳定剂及其制备方法
CN105295250A (zh) * 2015-11-18 2016-02-03 安徽华塑股份有限公司 一种pvc用水滑石马来酸锡复合环保稳定剂及其制备方法
CN105295251A (zh) * 2015-11-18 2016-02-03 安徽华塑股份有限公司 一种pvc用水滑石马来酸稀土复合环保稳定剂及其制备方法
CN105694295A (zh) * 2016-04-15 2016-06-22 佛山市聚成生化技术研发有限公司 一种pvc热稳定剂的制备方法及由该方法制备的热稳定剂
CN106317461A (zh) * 2016-08-23 2017-01-11 深圳市志海实业股份有限公司 一种插层聚合高效无毒环保钙锌稳定剂的合成制备方法
CN107011590B (zh) * 2017-03-07 2019-09-10 厦门理工学院 一种增韧耐增塑剂迁移聚氯乙烯材料及其制备方法、应用
CN109679243B (zh) * 2018-11-13 2022-04-01 广东联塑科技实业有限公司 一种耐热耐腐蚀聚氯乙烯给排水管及其制备方法
CN110204785B (zh) * 2019-06-24 2021-03-19 东莞市尚诺新材料有限公司 一种地板膜用稳定剂及其制备方法
CN114940779A (zh) * 2022-04-24 2022-08-26 衡水天星助剂有限公司 一种环保pvc透明钙锌热稳定剂
CN115746401A (zh) * 2022-06-20 2023-03-07 加通汽车内饰(常熟)有限公司 高氯酸盐改性水滑石及其常温下的制备方法、复合热稳定剂及其制备方法、皮革制品

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4299759A (en) * 1980-05-13 1981-11-10 Kyowa Chemical Industry Co. Ltd. Method for inhibiting the thermal or ultraviolet degradation of thermoplastic resin and thermoplastic resin composition having stability to thermal or ultraviolet degradation
EP0332514A1 (fr) * 1988-03-07 1989-09-13 M & T Chemicals, Inc. Composition utilisable pour la stabilisation thermique et ultraviolette de résines thermoplastiques et résines thermoplatiques contenant une telle composition stabilisante
JPH09324088A (ja) * 1996-06-06 1997-12-16 Furukawa Electric Co Ltd:The 塩化ビニル系樹脂組成物被覆電線
JP2000290451A (ja) * 1999-04-06 2000-10-17 Toda Kogyo Corp Ｍｇ−Ａｌ系ハイドロタルサイト型粒子粉末、塩素含有樹脂安定剤及びＭｇ−Ａｌ系ハイドロタルサイト型粒子粉末の製造法
JP2001098414A (ja) * 1999-09-28 2001-04-10 Toyo Chem Co Ltd 塩化ビニル系樹脂繊維

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4299759A (en) * 1980-05-13 1981-11-10 Kyowa Chemical Industry Co. Ltd. Method for inhibiting the thermal or ultraviolet degradation of thermoplastic resin and thermoplastic resin composition having stability to thermal or ultraviolet degradation
EP0332514A1 (fr) * 1988-03-07 1989-09-13 M & T Chemicals, Inc. Composition utilisable pour la stabilisation thermique et ultraviolette de résines thermoplastiques et résines thermoplatiques contenant une telle composition stabilisante
JPH09324088A (ja) * 1996-06-06 1997-12-16 Furukawa Electric Co Ltd:The 塩化ビニル系樹脂組成物被覆電線
JP2000290451A (ja) * 1999-04-06 2000-10-17 Toda Kogyo Corp Ｍｇ−Ａｌ系ハイドロタルサイト型粒子粉末、塩素含有樹脂安定剤及びＭｇ−Ａｌ系ハイドロタルサイト型粒子粉末の製造法
JP2001098414A (ja) * 1999-09-28 2001-04-10 Toyo Chem Co Ltd 塩化ビニル系樹脂繊維

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112694699A (zh) * 2020-12-22 2021-04-23 深圳市信维通信股份有限公司 一种含氟聚合物的应用及其制备方法

Also Published As

Publication number Publication date
CN1252159C (zh) 2006-04-19
CN1590437A (zh) 2005-03-09

Similar Documents

Publication Publication Date Title
WO2005105909A1 (fr) Stabilisant thermique composite a base d'hydrotalcite pour un haut polymere contenant du chlore
Du et al. Thermal properties and combustion characterization of nylon 6/MgAl-LDH nanocomposites via organic modification and melt intercalation
EP0933401B1 (fr) Composition de resine synthetique resistant a la deterioration thermique et pieces moulees
CN101942111B (zh) 一种锌镁铝水滑石基pvc复合热稳定剂的制造方法及应用
CN101492548B (zh) 一种pvc用复合热稳定剂及其制备和应用
CN105968412B (zh) 二茂铁改性三元类水滑石阻燃抑烟剂及其制备方法和用途
CN101538019B (zh) 疏水性纳米水滑石的制备方法
KR100200082B1 (ko) 합성금속 수산화물 및 이를 함유하는 물
CN101735532A (zh) 高耐候多效环保pvc复合热稳定剂及其制备方法
US6291570B1 (en) Heat deterioration resistant flame retardant, resin composition and molded article
CN101575425B (zh) 一种pvc用镁铝稀土类水滑石复合热稳定剂及其应用
CN101412912B (zh) 稀土复合阻燃剂及其制备方法
CN101544783A (zh) 疏水性纳米水滑石基pvc用复合热稳定剂及其制备方法
CN103237761A (zh) 高纵横比氢氧化镁
CN106674598A (zh) 一种高效改性层状双氢氧化物阻燃添加剂的制备方法
CN101508636A (zh) 一种乙酰丙酮基复合热稳定剂
CN102093654B (zh) Pvc用锌铝稀土类水滑石复合热稳定剂及其制备和应用
CN110862574A (zh) 高效抑烟的氢氧化镁/锡类化合物微胶囊阻燃剂及其制备方法
Yan et al. Intercalated hydrotalcite‐like materials and their application as thermal stabilizers in poly (vinyl chloride)
CN115716933B (zh) 一种聚合物用易分散型水滑石基复合材料及其制备方法
CN101967275A (zh) 纳米碳酸镁改性防火工程塑料及其制备方法
CN112457528A (zh) 一种层状双氢氧化物、三氧化二锑、十溴二苯乙烷复配阻燃剂及其制备方法
CN109897226A (zh) 超分子结构的钙羧酸插层紫外阻隔材料、制备方法、应用
WO2012139292A1 (fr) Composition de modifiant pour polyoléfine, polyoléfine pour emballage et film d'emballage souple
CN113444287B (zh) 一种改性水滑石及其制备方法、pvc热稳定剂及应用

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

122 Ep: pct application non-entry in european phase