[go: up one dir, main page]

WO2021072942A1 - Procédé de préparation de tartrate de zinc et son application dans un stabilisant - Google Patents

Procédé de préparation de tartrate de zinc et son application dans un stabilisant Download PDF

Info

Publication number
WO2021072942A1
WO2021072942A1 PCT/CN2019/123790 CN2019123790W WO2021072942A1 WO 2021072942 A1 WO2021072942 A1 WO 2021072942A1 CN 2019123790 W CN2019123790 W CN 2019123790W WO 2021072942 A1 WO2021072942 A1 WO 2021072942A1
Authority
WO
WIPO (PCT)
Prior art keywords
zinc
tartrate
stabilizer
zinc tartrate
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2019/123790
Other languages
English (en)
Chinese (zh)
Inventor
周国庆
周志鑫
严一丰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huizhou Aimsea Newway Technology Co Ltd
Original Assignee
Huizhou Aimsea Newway Technology Co Ltd
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 Huizhou Aimsea Newway Technology Co Ltd filed Critical Huizhou Aimsea Newway Technology Co Ltd
Publication of WO2021072942A1 publication Critical patent/WO2021072942A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the invention belongs to the field of stabilizer preparation, and specifically relates to a method for preparing zinc tartrate and its application in stabilizers.
  • the commonly used heat stabilizers are mainly divided into inorganic lead salts, metal soap salts, organic tin, and organic auxiliary heat stabilizers.
  • the most commonly used metal soap stabilizer is zinc soap stabilizer.
  • Zinc soap stabilizer can not only neutralize and absorb HCl, but also replace unstable chlorine atoms with carboxylate radicals to eliminate thermal degradation initiation sites, thus slowing down PVC. The removal of HCl can inhibit its initial coloring. However, zinc soap will produce ZnCl 2 due to the absorption of HCl.
  • the resulting ZnCl 2 has a strong catalytic effect, which will promote the further dehydrogenation of the polyene sequence, resulting in poor long-term thermal stability, and the ingredients will undergo malignant degradation soon after being heated.
  • the blackening and coking is also known as "zinc burn”.
  • Polyol compound is a commonly used auxiliary heat stabilizer.
  • the polyol compound contains multiple hydroxyl groups, and these hydroxyl groups can form a stable chelate with Zn 2+ , thereby inactivating its catalytic effect on the thermal degradation of PVC.
  • the more the number of hydroxyl groups contained in the molecule the more significant its effect of improving long-term thermal stability, but it will also lead to a decrease in its effect of inhibiting initial discoloration.
  • zinc content is an important factor affecting the initial color of PVC.
  • Most traditional zinc soap stabilizers are monobasic fatty acids, so one molecule of fatty acid zinc requires two molecules of monobasic fatty acid, which leads to the formation of zinc soap The higher the molecular weight, the lower the zinc content.
  • the dibasic fatty acid can be used to react with the zinc source, so that only one molecule of fatty acid can generate one molecule of zinc soap with one molecule of zinc source. The fatty acid chain will decrease and the zinc content will increase, thereby achieving an increase. The effect of initial whiteness.
  • the existing zinc soap stabilizers need to add polyol compounds to inhibit the late "zinc burning".
  • the mechanism of the polyol compound is to form a stable chelate compound with Zn 2+ through the hydroxyl group, thereby inactivating its catalytic effect on the thermal degradation of PVC. Therefore, the functional group that plays a key role in the polyol compound only needs to be a hydroxyl group.
  • the present invention starts from the above two aspects, looking for a dibasic acid with hydroxyl group, and tartaric acid (II) is one of them.
  • the molecular formula of tartaric acid (II) is C 4 H 6 O 4 , and the structural formula is It can be seen that tartaric acid (II) has two carboxyl groups and two hydroxyl groups.
  • the zinc tartrate (I) produced is both a zinc dibasic acid and two hydroxyl groups, which means that the zinc tartrate (I) not only has good initial coloring, but also can well inhibit the later "zinc burning".
  • the specific of the present invention The content is as follows:
  • One of the objectives of the present invention is to provide a structural formula such as (I):
  • the method for preparing zinc tartrate (I) is as follows:
  • step S2 Preparation of zinc tartrate (I): Weigh zinc sulfate heptahydrate and slowly add it to the Erlenmeyer flask described in step S1. The clear reaction liquid in step S1 becomes turbid, and continues to the triangle described in step S1. Deionized water is added to the flask, and the precipitate obtained by stirring while heating is the zinc tartrate (I).
  • the specific reaction equation is as follows:
  • the weight ratio of tartaric acid (II) and sodium hydroxide in the step S1 is 3 to 3.5:1, the reaction temperature is 70 to 80°C, and the reaction The time is 20-40min.
  • the acid in the step S1 is a hydrochloric acid solution with a substance concentration of 1 to 3 mol/L.
  • the weight ratio of step S2 zinc sulfate heptahydrate and tartaric acid (II) is 1.5 to 2.5:1, the reaction temperature is 100 to 120°C, and the reaction The time is 50 ⁇ 70min.
  • Another object of the present invention is to provide an application of zinc tartrate (I) in a stabilizer.
  • the technical point is: the zinc tartrate (I) is added to the stabilizer, and the addition amount of the zinc tartrate (I) is It is 5.5 ⁇ 6.5wt%.
  • the stabilizer is composed of calcium stearate, zinc stearate, zinc tartrate (I), zeolite, tris(2-hydroxyethyl) isocyanurate, and maleic acid. It is prepared by mixing di-n-butyl acid, calcium acetylacetonate, n-octadecyl propionate, pentaerythritol, perchlorate, internal lubricant and external lubricant.
  • the weight ratio of zinc stearate and zinc tartrate (I) is 0-1:1.
  • the present invention has the following beneficial effects:
  • a preparation method of zinc tartrate (I) according to the present invention wherein zinc tartrate (I) is used instead of the traditional zinc salt stabilizer and applied in the PVC production formula.
  • the traditional zinc stearate has a molecular weight of 632 and a zinc content of 10.3%, while the molecular weight of zinc tartrate (I) is 249.5. Its zinc content is 26.2%.
  • the zinc dibasic acid proposed in the present invention has a very high Zinc content, which can significantly improve the initial whiteness of the product.
  • the zinc tartrate (I) prepared by the present invention also has two hydroxyl groups. When the zinc tartrate (I) absorbs HCl, it will generate ZnCl 2 and tartaric acid (II).
  • the reaction equation is as follows:
  • Figure 1 is a flow chart of a method for preparing zinc tartrate (I) of the present invention.
  • the preparation method of zinc tartrate (I) is as follows:
  • Zinc tartrate (I) preparation Weigh 57.5g zinc sulfate heptahydrate, and slowly add it to the Erlenmeyer flask described in step S1, the clear reaction liquid in step S1 becomes turbid, and continues to step S1 Add deionized water to the Erlenmeyer flask, heat it to 110°C, and react for 60 minutes. The precipitate obtained is the zinc tartrate (I). The product is taken out, filtered, washed and dried, and the zinc content is determined to be 27.58%.
  • the specific reaction equation is as follows :
  • Zinc tartrate (I) is added to the stabilizer.
  • the specific formula is shown in Table 1.
  • the mass of the added tartaric acid is 5g.
  • the preparation method of zinc tartrate (I) is as follows:
  • Zinc tartrate (I) preparation Weigh 45g zinc sulfate heptahydrate, and slowly add it to the Erlenmeyer flask described in step S1, the clear reaction liquid in step S1 becomes turbid, and continues to the step S1 Add deionized water to the Erlenmeyer flask, heat to 100°C, and react for 70 min. The precipitate obtained is the zinc tartrate (I).
  • the specific reaction equation is as follows:
  • Zinc tartrate (I) is added to the stabilizer.
  • the specific formula is shown in Table 1.
  • the mass of the added tartaric acid is 5g.
  • the preparation method of zinc tartrate (I) is as follows:
  • Zinc tartrate (I) preparation Weigh 75g zinc sulfate heptahydrate, and slowly add it to the Erlenmeyer flask described in step S1, the clear reaction liquid in step S1 becomes turbid, and continues to the step S1 Add deionized water to the Erlenmeyer flask, heat to 120°C, and react for 50 minutes. The precipitate obtained is the zinc tartrate (I). The product is filtered, washed and dried, and the zinc content is determined to be 28.05%.
  • the specific reaction equation is as follows:
  • An application of zinc tartrate (I) in a stabilizer is to add zinc tartrate (I) to the stabilizer.
  • the specific formula is shown in Table 1.
  • the weight of the added tartaric acid is 5g.
  • the components of each group were stirred uniformly in a disperser, and then mixed on an open rubber mixing machine at a temperature of 190 ⁇ 2°C and a mixing time of 3 minutes to prepare PVC flakes.
  • the prepared PVC sheet samples were made into 10 small pieces of 16mm ⁇ 24mm, placed on aluminum foil, and placed in a 401A aging test box at a temperature of 190 ⁇ 1°C. One piece was taken out every 10 minutes to test its yellowness.
  • Table 3 The results are shown in Table 3:
  • the zinc tartrate (I) prepared by the method of the present invention can significantly improve the initial whiteness of PVC products and can effectively reduce the occurrence of "zinc burn" phenomenon, so the present invention has great prospects.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)

Abstract

La présente invention concerne un procédé de préparation du tartrate de zinc (I) représenté par la formule développée (I). Le procédé consiste à : premièrement, faire réagir l'acide tartrique (II) avec de l'hydroxyde de sodium pour préparer du tartrate de sodium (III), puis faire réagir le tartrate de sodium (III) préparé avec du sulfate de zinc heptahydraté pour obtenir le tartrate de zinc (I). Le tartrate de zinc (I) préparé peut être ajouté à un stabilisant, et la quantité d'addition du tartrate de zinc (I) est de 5,5 à 6,5 % en poids. Dans la présente invention, la teneur en zinc du tartrate de zinc (I) est de 26,2 %, et la blancheur initiale du produit peut être améliorée de manière significative.
PCT/CN2019/123790 2019-10-14 2019-12-06 Procédé de préparation de tartrate de zinc et son application dans un stabilisant Ceased WO2021072942A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910973200.8 2019-10-14
CN201910973200.8A CN110668934A (zh) 2019-10-14 2019-10-14 一种酒石酸锌的制备方法及其在稳定剂中的应用

Publications (1)

Publication Number Publication Date
WO2021072942A1 true WO2021072942A1 (fr) 2021-04-22

Family

ID=69082309

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/123790 Ceased WO2021072942A1 (fr) 2019-10-14 2019-12-06 Procédé de préparation de tartrate de zinc et son application dans un stabilisant

Country Status (2)

Country Link
CN (1) CN110668934A (fr)
WO (1) WO2021072942A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115505171A (zh) * 2022-09-27 2022-12-23 浙江工业大学 一种新型有机锌盐pvc复配热稳定剂及其制备方法与应用
CN115505170A (zh) * 2022-10-11 2022-12-23 青岛厚德天圆创新科技有限公司 一种锌烧抑制剂及其制备方法
CN116622129A (zh) * 2023-07-24 2023-08-22 山东和瑞新材料科技有限公司 一种pvc用钙锌稳定剂

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005108339A2 (fr) * 2004-05-06 2005-11-17 Osteologix A/S Procedes de synthese rapide et a haut rendement destines a produire des sels organometalliques
CN101687338A (zh) * 2007-01-17 2010-03-31 詹尼克斯公司 用于木材及类似材料的防腐剂组合物
CN101942110A (zh) * 2010-09-06 2011-01-12 芜湖海螺型材科技股份有限公司 一种钙锌复合稳定剂
CN105906520A (zh) * 2016-05-19 2016-08-31 浙江野风药业股份有限公司 一种左旋甲基多巴中间体的回收方法及应用
CN106380729A (zh) * 2016-08-30 2017-02-08 邵卫东 新型pvc热稳定剂

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102093207B (zh) * 2010-12-07 2012-09-19 浙江大学 一种无定形的掺Sb-酒石酸锌微纳球及其制备方法
RU2550361C1 (ru) * 2014-05-27 2015-05-10 Игорь Иванович Зоткин Соль цинка или меди (ii) и ее применение в качестве биоцида

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005108339A2 (fr) * 2004-05-06 2005-11-17 Osteologix A/S Procedes de synthese rapide et a haut rendement destines a produire des sels organometalliques
CN101687338A (zh) * 2007-01-17 2010-03-31 詹尼克斯公司 用于木材及类似材料的防腐剂组合物
CN101942110A (zh) * 2010-09-06 2011-01-12 芜湖海螺型材科技股份有限公司 一种钙锌复合稳定剂
CN105906520A (zh) * 2016-05-19 2016-08-31 浙江野风药业股份有限公司 一种左旋甲基多巴中间体的回收方法及应用
CN106380729A (zh) * 2016-08-30 2017-02-08 邵卫东 新型pvc热稳定剂

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PALOIC, ANA ET AL.,: "Structural and Degradation Studies of a Biocompatible Zn-L-Tartrate Metal-Organic Framework,", JOURNAL OF SOLID STATE CHEMISTRY., no. 225, 8 December 2014 (2014-12-08), XP029583524, ISSN: 0022-4596, DOI: 10.1016/j.jssc.2014.11.028 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115505171A (zh) * 2022-09-27 2022-12-23 浙江工业大学 一种新型有机锌盐pvc复配热稳定剂及其制备方法与应用
CN115505171B (zh) * 2022-09-27 2023-09-05 浙江工业大学 一种新型有机锌盐pvc复配热稳定剂及其制备方法与应用
CN115505170A (zh) * 2022-10-11 2022-12-23 青岛厚德天圆创新科技有限公司 一种锌烧抑制剂及其制备方法
CN116622129A (zh) * 2023-07-24 2023-08-22 山东和瑞新材料科技有限公司 一种pvc用钙锌稳定剂
CN116622129B (zh) * 2023-07-24 2023-09-12 山东和瑞新材料科技有限公司 一种pvc用钙锌稳定剂

Also Published As

Publication number Publication date
CN110668934A (zh) 2020-01-10

Similar Documents

Publication Publication Date Title
WO2021072942A1 (fr) Procédé de préparation de tartrate de zinc et son application dans un stabilisant
CN108892631B (zh) 一种用于pvc的热稳定剂及其合成方法
CN113717438A (zh) 一种具有紫外光屏蔽作用的钙锌稳定剂及其制备方法
CN107163286B (zh) 一种pvc用含锌热稳定剂及其制备方法与应用
WO2018072262A1 (fr) Co-stabilisant pvc polythioéther, son procédé de préparation et son application
CN112608570B (zh) 一种聚氯乙烯辅助热稳定剂及其制备方法
CN104828866B (zh) 一种高温下低挥发的胶体氧化锑干粉及其制备方法
CN110358221B (zh) Pvc用山梨酸镧复合热稳定剂
CN116262989A (zh) 一种纳米氧化锌改性阻燃抗菌聚酯纤维及其制备方法
CN105131451B (zh) 一种季戊四醇苯基碳酸酯型pvc复合热稳定剂及应用
CN118027518A (zh) 一种pvc用钙锌复合稳定剂及其制备方法
CN104893184B (zh) 一种含锌羟基磷灰石基pvc复合热稳定剂及应用
CN107501119B (zh) 一种固相法制备pvc稀土热稳定剂的方法
CN111393553B (zh) 一种有机低聚物的制备方法和含有该有机低聚物的有机复合热稳定剂及其应用
CN119192677B (zh) 一种pvc用复合热稳定剂及制备方法
CN110423417B (zh) 硬质pvc用有机锡酸插层钙/锌铝稀土类水滑石复合热稳定剂及其制备方法
CN111423733A (zh) 一种新型乳清酸镧复合pvc热稳定剂
CN106519304B (zh) 一种分子筛负载型聚氯乙烯热稳定剂及其制备方法
CN119735902B (zh) 一种耐老化聚氯乙烯片材及其制备方法
CN115403830B (zh) 一种用于pvc热稳定剂的改性水滑石的制备方法
CN112574520A (zh) 一种透明环保稳定剂及其制备方法
CN119708623B (zh) 一种热稳定剂及其制备方法
CN117801309A (zh) 一种多孔配位聚合物复合型pvc热稳定剂的制备方法
CN112940345A (zh) 一种降低pvc凝胶化温度复合热稳定剂及其制备方法
CN110330686A (zh) 稀土复合稳定剂及其制备方法和应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19949167

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19949167

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 19949167

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 10/10/2022)

122 Ep: pct application non-entry in european phase

Ref document number: 19949167

Country of ref document: EP

Kind code of ref document: A1