CN101775153A - Barium-zinc liquid stabilizer, preparation method and application thereof - Google Patents
Barium-zinc liquid stabilizer, preparation method and application thereof Download PDFInfo
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- CN101775153A CN101775153A CN201010104069A CN201010104069A CN101775153A CN 101775153 A CN101775153 A CN 101775153A CN 201010104069 A CN201010104069 A CN 201010104069A CN 201010104069 A CN201010104069 A CN 201010104069A CN 101775153 A CN101775153 A CN 101775153A
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Abstract
The invention relates to PVC heat stabilizer, in particular to heat stabilizer applied to decoration of PVC materials, a preparation method and application thereof. The barium-zinc liquid stabilizer is prepared from the following components in percentage by weight:, 20.0 to 35.0 percent of sodium iso-octoate, 10.0 to 15.5 percent of oleic acid, 8.5 to 12.8 percent of barium monohydrate, 1.0 to 5.0 percent of zinc oxide, 5.0 to 10.5 percent of diethylene glycolmonobutylether, 1.0 to 3.0 percent of antioxidant 1010, 1.0 to 4.5 percent of bisphenol A, 1.0 to 3.0 percent of beta-diketone, 5.0 to 10.5 percent of anti-separation agent, and 20.0 to 35.0 percent of DOP, wherein the total amount of components is 100 percent. The invention solves the problem that products have foreign smell based on raw materials, simplifies the production process by a one-step synthesis method, has more convenient operation, and has the effects that: firstly, the stabilizer saves energy consumption and reducing pollution; secondly, the stabilizer has high value advantage compared with international products with the same function and has better competitive force; and thirdly, the stabilizer belongs to green and environment-friendly product, and has strong vitality.
Description
Technical field
The present invention relates to a kind of PVC thermo-stabilizer, relate in particular to a kind of thermo-stabilizer that is applied to decoration of PVC materials and its production and application.
Background technology
Thermo-stabilizer is that a class can prevent or reduce polymkeric substance and is heated in the use and degraded or crosslinked takes place in processing, prolongs the matrix material additive in work-ing life.Stablizer commonly used can be divided into salt base class, fatty acid soaps class, organo-tin compound, composite type heat stablizer and pure organic compound class according to the main component classification.
1) alkali type thermal stabilizing agent: salt base class stablizer is meant and is combined with the inorganic of " alkali " and organic acid lead salt, this class stablizer has good thermotolerance, weathering resistance and electrical insulating property, and cost is low, and the transparency is poor, certain toxicity is arranged, and consumption is generally 0.5%～5.0%.
2) fatty acid thermo-stabilizer: this type thermal stabilizing agent is meant the compound of being made up of fatty acid radical and metal ion, also claims metal soap thermal stabilizers, and its performance is relevant with the kind of acid group and metal ion, and general consumption is 0.1%～3.0%.
3) organic tin thermo-stabilizer: this type thermal stabilizing agent can form ligand with unstable chlorine atom in the polyvinyl chloride molecule, and in ligand the carboxylic acid ester groups and the unsettled chlorine atomic substitutions of organotin.The characteristics of this type thermal stabilizing agent are that stability is high, good, the excellent heat resistance of the transparency, and weak point is that price is more expensive.
4) composite type heat stablizer: this type thermal stabilizing agent is based on the liquid or solid mixture of salt base class or metallic soap class and the mixture of organotin, and wherein metallic salt has calcium-magnesium-zinc, barium-calcium-zinc, barium-zinc and barium-cadmium etc.; Organic acid such as organic lipid acid, naphthenic acid, oleic acid, phenylformic acid and Whitfield's ointment etc. commonly used.
5) organic compound thermo-stabilizer: the main stabilizer that this type thermal stabilizing agent can use separately except that minority (mainly being nitrogenous organic compound), also comprise high boiling polyvalent alcohol and phosphorous acid ester, phosphorous acid ester normal and metal(lic)stabilizer and usefulness, can improve weathering resistance, the transparency of matrix material, improve the surface color of goods.
The mechanism of action of PVC thermo-stabilizer is as follows: in 1) absorbing and HCL, suppress its autocatalytic action.This class stablizer comprises lead salts, organic acid metal soap class, organo-tin compound, epoxy compounds, phenates and metal mercaptide salt etc.They can react with HCL, suppress the reaction that PVC takes off HCL.2) unsettled chlorallylene atom suppresses to take off PVC in the displacement PVC molecule.Combine with the unstable chlorine atom generation coordination of PVC molecule as organotin stabilizer, in ligand, organotin and unstable chlorine atomic substitutions.3) with polyene structure generation addition reaction, destroy the formation of big conjugated system, reduce painted.The salt of unsaturated acid or ester contain two keys, with conjugated double bond generation diene addition reaction in the PVC molecule, thereby destroy its conjugated structure, suppress variable color.
The composite type heat stablizer is because good performance and favorable environment protection can be the trend of development, and the existing PVC thermo-stabilizer that is used for top layer film in the car adopts raw material: phosphorous acid ester, 1010, dihydroxyphenyl propane, β--diketone, white oil, solvent oil, anti-precipitation agent, hydrated barta, zinc oxide, oleic acid, isocaprylic acid, triglycol, nonyl phenol; Production technique comprises the steps: 1. hydrated barta, nonyl phenol, triglycol, oleic acid etc. to be made 6# barium; 2. isocaprylic acid, oleic acid, zinc oxide, phosphorous acid ester, white oil etc. are made 4# zinc; 3. with 6# barium, 4# zinc and phosphorous acid ester, 1010, dihydroxyphenyl propane, β--diketone, white oil, solvent oil, anti-precipitation agent mix, and stir to get final product in 1 hour under 120 ℃ of temperature.This product preparation process complexity, and product has peculiar smell.
Summary of the invention
For the technological deficiency that the PVC thermo-stabilizer that solves top layer film in the above-mentioned car exists, first purpose of the present invention provides a kind of barium-zinc liquid stabilizer, and this stablizer solves the problem that product has peculiar smell, has the characteristics of safety and environmental protection.Another object of the present invention provides the preparation method of above-mentioned barium-zinc liquid stabilizer, and this method has been simplified production process, operates easier.
In order to realize first above-mentioned purpose, the present invention has adopted following technical scheme:
A kind of barium-zinc liquid stabilizer, this liquid stabilisers is prepared by following component by weight percentage:
As preferably, this liquid stabilisers is prepared by following component by weight percentage:
As preferred again, this liquid stabilisers is prepared by following component by weight percentage:
In order to realize second above-mentioned purpose, the preparation method of barium-zinc liquid stabilizer of the present invention, this method comprises the steps:
1. isocaprylic acid, oleic acid, barium monohydrate, zinc oxide and part Diethylene Glycol butyl ether are put into reactor, stir and are warming up to 80～95 ℃, and insulation is to fully anti-;
2. question response is complete, after solution becomes is transparent, is warming up to 100～110 ℃, carries out vacuum hydro-extraction;
3. after the vacuum hydro-extraction, add antioxidant 1010, dihydroxyphenyl propane, β--diketone, anti-precipitation agent, DOP and remaining Diethylene Glycol butyl ether, stir under 115～125 ℃ of temperature and got final product in 0.5～2 hour.
As preferably, 1. above-mentioned steps is 1: 2～2: 3 with the mass ratio that 3. step adds the Diethylene Glycol butyl ether.
The present invention also discloses top layer PVC film in a kind of car in addition, and this PVC film adopts barium-zinc liquid stabilizer of the present invention.The usage quantity of barium-zinc liquid stabilizer of the present invention is identical with the usage quantity of existing liquid stabilisers.
The present invention is owing to having adopted above-mentioned technical scheme, and is compound with other auxiliary stabilizer again behind organic acid and metal oxide and oxyhydroxide effect generation metallic soap, forms one package stabilizer efficiently at last.Wherein, isocaprylic acid, oleic acid are organic acid, and barium monohydrate is an oxyhydroxide, and zinc oxide is metal oxide, and the Diethylene Glycol butyl ether is made thinner, 1010, dihydroxyphenyl propane is oxidation inhibitor, and β--diketone is an auxiliary stabilizer, and the effect of reduction " zinc burning " can be arranged.DOP makees solvent, and anti-precipitation agent is that market purchasing mainly is the blending that improves stablizer and resin, and minimizing is oozed out.
Product of the present invention is compared with existing like product, and the present invention solves the problem that product has peculiar smell from raw material, simultaneously, has simplified production process, and adopt in the past and divide step production method, be one-step synthesis now, operate easier.Product of the present invention is with respect to existing products, and effect of the present invention is obvious.Mainly show: the first, energy efficient has also reduced pollution.The second, we have very big price advantage with the product of congenerous is compared in the world, therefore also have more competitive power.The 3rd, also be the most outstanding a bit to the invention belongs to Green Product, have very strong vitality.
Embodiment
The following specific embodiments of the present invention is to make a detailed explanation.
Embodiment 1
A kind of barium-zinc liquid stabilizer, the raw materials by weight meter of this liquid stabilisers is made up of following component:
| Isocaprylic acid | 28.5% | Oleic acid | 12.5% |
| Barium monohydrate | 9.8% | Zinc oxide | 4.2% |
| The Diethylene Glycol butyl ether | 6.5% | Antioxidant 1010 | 1.5% |
| Dihydroxyphenyl propane | 3.5% | β--diketone | 2.0% |
| Anti-precipitation agent | 7.5% | DOP | 24.0%. |
The preparation method of above-mentioned barium-zinc liquid stabilizer, this method comprises the steps:
1. isocaprylic acid, oleic acid, barium monohydrate, zinc oxide and part Diethylene Glycol butyl ether are put into reactor, stir and are warming up to 90 ℃, are incubated 2 hours to fully anti-;
2. question response is complete, after solution becomes is transparent, is warming up to 100 ℃, carries out vacuum hydro-extraction;
3. dewatering after about half an hour, add antioxidant 1010, dihydroxyphenyl propane, β--diketone, anti-precipitation agent, DOP and remaining Diethylene Glycol butyl ether, stirring got final product in 1 hour under 120 ℃ of temperature.
Wherein: 1. step is 1: 2 with the mass ratio that 3. step adds the Diethylene Glycol butyl ether.
Embodiment 2
A kind of barium-zinc liquid stabilizer, the raw materials by weight meter of this liquid stabilisers is made up of following component:
| Isocaprylic acid | 21.8% | Oleic acid | 14.2% |
| Barium monohydrate | 11.2% | Zinc oxide | 3.5% |
| The Diethylene Glycol butyl ether | 9.6% | Antioxidant 1010 | 2.4% |
| Dihydroxyphenyl propane | 1.8% | β--diketone | 2.4% |
| Anti-precipitation agent | 6.2% | DOP | 26.9%. |
The preparation method of above-mentioned barium-zinc liquid stabilizer, this method comprises the steps:
1. isocaprylic acid, oleic acid, barium monohydrate, zinc oxide and part Diethylene Glycol butyl ether are put into reactor, stir and are warming up to 90 ℃, are incubated 2 hours to fully anti-;
2. question response is complete, after solution becomes is transparent, is warming up to 100 ℃, carries out vacuum hydro-extraction;
3. dewatering after about half an hour, add antioxidant 1010, dihydroxyphenyl propane, β--diketone, anti-precipitation agent, DOP and remaining Diethylene Glycol butyl ether, stirring got final product in 1 hour under 120 ℃ of temperature.
Wherein: 1. step is 2: 3 with the mass ratio that 3. step adds the Diethylene Glycol butyl ether.
Embodiment 3
A kind of barium-zinc liquid stabilizer, the raw materials by weight meter of this liquid stabilisers is made up of following component:
| Isocaprylic acid | ??27.3％ | Oleic acid | ??13.5％ |
| Barium monohydrate | ??9.2％ | Zinc oxide | ??2.3％ |
| The Diethylene Glycol butyl ether | ??7.2％ | Antioxidant 1010 | ??1.8％ |
| Dihydroxyphenyl propane | ??2.4％ | β--diketone | ??2.0％ |
| Anti-precipitation agent | ??7.3％ | ??DOP | ??27.0％； |
The preparation method of above-mentioned barium-zinc liquid stabilizer, this method comprises the steps:
1. isocaprylic acid, oleic acid, barium monohydrate, zinc oxide and part Diethylene Glycol butyl ether are put into reactor, stir and are warming up to 90 ℃, are incubated 2 hours to fully anti-;
2. question response is complete, after solution becomes is transparent, is warming up to 100 ℃, carries out vacuum hydro-extraction;
3. dewatering after about half an hour, add antioxidant 1010, dihydroxyphenyl propane, β--diketone, anti-precipitation agent, DOP and remaining Diethylene Glycol butyl ether, stirring got final product in 1 hour under 120 ℃ of temperature.
Wherein: 1. step is 3: 5 with the mass ratio that 3. step adds the Diethylene Glycol butyl ether.
Test example 1
The product that the embodiment of the invention 3 prepares and German bear board 801S barium-zinc liquid stabilizer stability contrast table such as table 1.
Table 1: stablizer stability contrast table
By table 1 as can be seen, the stability of the stablizer of the inventive method preparation is better than the advanced like product of import.Moreover stablizer of the present invention by experiment is placed on baking oven taking-up after interior 2 hours of 80 ℃ with frosted bottle splendid attire, and is tasteless.Compare with the 801S of German bear board, product flavor of the present invention is lighter, thereby we can say that the present invention not only can substitute the import like product, but also has remedied domestic blank market.
Claims (6)
1. barium-zinc liquid stabilizer is characterized in that this liquid stabilisers is prepared by following component by weight percentage:
2. a kind of barium-zinc liquid stabilizer according to claim 1 is characterized in that this liquid stabilisers is prepared by following component by weight percentage:
3. a kind of barium-zinc liquid stabilizer according to claim 1 is characterized in that this liquid stabilisers is prepared by following component by weight percentage:
4. the preparation method as claim 1 or 2 or 3 described barium-zinc liquid stabilizers is characterized in that this method comprises the steps:
1. isocaprylic acid, oleic acid, barium monohydrate, zinc oxide and part Diethylene Glycol butyl ether are put into reactor, stir and are warming up to 80～95 ℃, and insulation is to fully anti-;
2. question response is complete, after solution becomes is transparent, is warming up to 100～110 ℃, carries out vacuum hydro-extraction;
3. after the vacuum hydro-extraction, add antioxidant 1010, dihydroxyphenyl propane, β--diketone, anti-precipitation agent, DOP and remaining Diethylene Glycol butyl ether, stir under 115～125 ℃ of temperature and got final product in 0.5～2 hour.
5. the preparation method of barium-zinc liquid stabilizer according to claim 4 is characterized in that: 1. step is 1: 2～2: 3 with the mass ratio that 3. step adds the Diethylene Glycol butyl ether.
6. top layer PVC film in the car, it is characterized in that: this PVC film adopts as claim 1 or 2 or 3 described barium-zinc liquid stabilizers.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604263A (en) * | 2012-03-13 | 2012-07-25 | 德清县东来化学有限公司 | Potassium-zinc liquid stabilizer for PVC (polyvinyl chloride) wallpaper and preparation method of potassium-zinc liquid stabilizer |
| CN102604264A (en) * | 2012-03-13 | 2012-07-25 | 德清县东来化学有限公司 | Potassium-zinc liquid stabilizer for PVC (polyvinyl chloride) artificial leather and preparation method for same |
| CN103304847A (en) * | 2013-07-02 | 2013-09-18 | 上海浩缘环保材料有限公司 | Barium-zinc liquid stabilizer and preparation method thereof |
| CN103450589A (en) * | 2013-08-16 | 2013-12-18 | 泰山体育产业集团有限公司 | Liquid compound stabilizer for PVC (Polyvinyl Chloride) and preparation method thereof |
| CN104910414A (en) * | 2015-06-18 | 2015-09-16 | 巢湖香枫塑胶助剂有限公司 | Preparation method of liquid barium-zinc composite heat stabilizer |
| CN106084538A (en) * | 2016-06-14 | 2016-11-09 | 浙江海普顿新材料股份有限公司 | A kind of liquid carboxylic slaine and preparation method and application |
| CN107141643A (en) * | 2017-05-26 | 2017-09-08 | 南通艾德旺化工有限公司 | A kind of barium-zinc liquid heat stabilizer and preparation method thereof, application |
| CN109293988A (en) * | 2018-10-07 | 2019-02-01 | 德清县东来化学有限公司 | A kind of environment-friendly liquid barium zinc compound stabilizer and preparation method thereof |
| CN110066522A (en) * | 2019-04-25 | 2019-07-30 | 安徽华文塑胶科技有限公司 | Anti- precipitation liquid stabilizer of one kind and preparation method thereof |
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2010
- 2010-01-28 CN CN2010101040690A patent/CN101775153B/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102604263A (en) * | 2012-03-13 | 2012-07-25 | 德清县东来化学有限公司 | Potassium-zinc liquid stabilizer for PVC (polyvinyl chloride) wallpaper and preparation method of potassium-zinc liquid stabilizer |
| CN102604264A (en) * | 2012-03-13 | 2012-07-25 | 德清县东来化学有限公司 | Potassium-zinc liquid stabilizer for PVC (polyvinyl chloride) artificial leather and preparation method for same |
| CN103304847A (en) * | 2013-07-02 | 2013-09-18 | 上海浩缘环保材料有限公司 | Barium-zinc liquid stabilizer and preparation method thereof |
| CN103450589A (en) * | 2013-08-16 | 2013-12-18 | 泰山体育产业集团有限公司 | Liquid compound stabilizer for PVC (Polyvinyl Chloride) and preparation method thereof |
| CN103450589B (en) * | 2013-08-16 | 2016-08-10 | 泰山体育产业集团有限公司 | A kind of PVC liquid composite stabilizing agent and preparation method thereof |
| CN104910414A (en) * | 2015-06-18 | 2015-09-16 | 巢湖香枫塑胶助剂有限公司 | Preparation method of liquid barium-zinc composite heat stabilizer |
| CN106084538A (en) * | 2016-06-14 | 2016-11-09 | 浙江海普顿新材料股份有限公司 | A kind of liquid carboxylic slaine and preparation method and application |
| CN107141643A (en) * | 2017-05-26 | 2017-09-08 | 南通艾德旺化工有限公司 | A kind of barium-zinc liquid heat stabilizer and preparation method thereof, application |
| CN107141643B (en) * | 2017-05-26 | 2019-06-07 | 南通艾德旺化工有限公司 | A kind of barium-zinc liquid heat stabilizer and preparation method thereof, application |
| CN109293988A (en) * | 2018-10-07 | 2019-02-01 | 德清县东来化学有限公司 | A kind of environment-friendly liquid barium zinc compound stabilizer and preparation method thereof |
| CN110066522A (en) * | 2019-04-25 | 2019-07-30 | 安徽华文塑胶科技有限公司 | Anti- precipitation liquid stabilizer of one kind and preparation method thereof |
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