CN103694599A - Efficient and environment-friendly polyvinyl chloride heat stabilizer and preparation method thereof - Google Patents
Efficient and environment-friendly polyvinyl chloride heat stabilizer and preparation method thereof Download PDFInfo
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- CN103694599A CN103694599A CN201310665356.2A CN201310665356A CN103694599A CN 103694599 A CN103694599 A CN 103694599A CN 201310665356 A CN201310665356 A CN 201310665356A CN 103694599 A CN103694599 A CN 103694599A
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Abstract
The invention relates to an efficient and environment-friendly polyvinyl chloride heat stabilizer. The heat stabilizer is prepared by the following components in parts by mass: 50-80 parts of Ca/Zn inorganic compound soap salt, 2-14 parts of hydrotalcite, 1-9 parts of phosphorous acid vinegar, 10-20 parts of beta-diketone, and 1-7 parts of paraffin. Furthermore, the invention also discloses a preparation method for the stabilizer. The stabilizer can effectively improve stabilization efficiency and pigmenting property, has no toxicity and is environmentally friendly.
Description
Technical field
The present invention relates to a kind of inorganic type thermo-stabilizer and synthesis and preparation process thereof using in the course of processing of PVC plastics, relate in particular to a kind of efficient, environment-friendly polyvinyl chloride thermo-stabilizer and preparation method thereof.
Background technology
In recent years, although the pros and cons of development polyvinyl chloride (PVC) are had to different views, PVC is still output and consumption in the world and is only second to one of polyacrylic five large synthetic resins up to now.Be heated in the course of processing effect of oxygen and shearing force of PVC can remove hydrogenchloride and forms free radical and peroxy radical and triggered degradation, and its degraded demonstrates corresponding characteristic color.For effectively suppressing product appearance color and luster that this degraded causes and the decline of mechanical property, thermo-stabilizer becomes the indispensable main auxiliary agent of PVC processing.
With the fast development of PVC industry, market also increases considerably the demand of thermo-stabilizer.Yet due to reasons such as the levels of economic development, China is mainly used Lead salt thermal stabilizer for a long time, and non-toxic heat stabilizer is less than 15%.Yet research finds that lead salt, as a kind of poisonous metal compound, is easy to be extracted out from PVC goods by water and solvent, damages thereby enter by all means human body.Lead is typical many affinitys poisonous substance, has in vivo cumulative effect, in blood, can form alkali lead sulfate, and is present in bone with stable form, and various organizing all had to toxic action.Therefore, PVC thermo-stabilizer without poisoning, high efficiency problem become one of important topic urgently to be resolved hurrily.
Summary of the invention
Technical problem to be solved by this invention is to provide efficient, the environment-friendly polyvinyl chloride thermo-stabilizer of a kind of effective raising stabilization efficiency and tinctorial property.
Another technical problem to be solved by this invention is to provide that this is efficient, the preparation method of environment-friendly polyvinyl chloride thermo-stabilizer.
For addressing the above problem, a kind of efficient, environment-friendly polyvinyl chloride thermo-stabilizer of the present invention, is characterized in that: this stablizer is assigned to make by following quality group: 50 ~ 80 parts of Ca/Zn inorganic compounding soap salt, 2 ~ 14 parts of hydrotalcites, 1 ~ 9 part of phosphorous acid vinegar, 10 ~ 20 parts of beta-diketons, 1 ~ 7 part, paraffin.
Described Ca/Zn inorganic compounding soap salt refers to when 25 ~ 150mL lipid acid is slowly warming up to 55 ~ 65 ℃ under at the uniform velocity stirring, add 4 ~ 20 g Glacial acetic acid, 1.5 ~ 7.5 g vitriol oils, and to start to drip mass concentration be 20% ~ 30% hydrogen peroxide 10 ~ 45 mL, 1 h dropwises, and in temperature, be to continue stirring reaction 3 h under the condition of 55 ~ 65 ℃, generate epoxyoleic acid; Described epoxyoleic acid washes with water to neutrality, carries out vacuum hydro-extraction in vacuum tightness under the condition that is 0.1 ~ 0.2MPa, obtains the epoxyoleic acid that dewaters; After described dehydration epoxyoleic acid is heated to 70 ~ 80 ℃, add 5.6 ~ 28g calcium hydroxide, 14.4 ~ 72 g zinc oxide, 1 ~ 5g strongly acidic cation-exchange, stir and get final product.
Described paraffin refers to that molecular weight is the low molecular weight polyethylene wax of 1500-25000.
The preparation method of a kind of efficient, environment-friendly polyvinyl chloride thermo-stabilizer as above, it is characterized in that: first by proportioning, weigh, then in Ca/Zn inorganic compounding soap salt, add successively hydrotalcite, phosphorous acid vinegar, beta-diketon, paraffin to react, reacted rear filtration, obtain complex Ca/Zn stablizer crude product, this complex Ca/Zn stablizer crude product is section according to a conventional method after being dried to constant weight under the condition of 25 ~ 35 ℃ in temperature, obtains calcium-zinc composite stabilizing agent product.
A kind of efficient, the application of environment-friendly polyvinyl chloride thermo-stabilizer in preparing polrvinyl chloride product as above, is characterized in that: the add-on of this polychloroethylene heat stabilizer is 2% ~ 11% of polyvinyl chloride quality.
The present invention compared with prior art has the following advantages:
1, owing to containing beta-diketon in the present invention, can there is C-alkylation substitution reaction with unsettled chlorallylene in PVC in it, form firmly carbon-to-carbon structure fast, and therefore, the present invention has effectively improved stabilization efficiency and tinctorial property.
2, owing to adopting Ca/Zn soap salt to replace traditional Organic heavy metal salt in the present invention, therefore, the present invention is nontoxic, environmental protection, has reduced the pollution to environment.
3, owing to containing the metallic element Zn that electronegativity is larger in the present invention, can form coordinate bond with unsettled allyl group in polyvinyl chloride resin, and the negatively charged ion that makes metallic soap replaces unstable chlorine atom, alleviate PVC and removed the speed of reaction that hydrogenchloride is sent out DeR, therefore, the present invention has reduced the degradation speed of PVC plastics.
4, the present invention adopts the Congo's red heat laboratory method, heat baking laboratory method to investigate to the thermostable effect of PVC plastics, can find out: the present invention is efficient, the polychloroethylene heat stabilizer thermostability of environmental protection is compared with traditional Ca/Zn thermo-stabilizer its stability improve a lot (referring to table 1).Experimental technique is as follows:
By thermo-stabilizer, by the mixing that feeds intake of the formula rate of PVC 120 g, the present invention 30 g, mixed raw material is added on double roller plastic-making device, and at 180 ~ 200 ℃, mixing 5 min are in blocks.The sheet specimens that the PVC test piece making is cut into l cm * l cm, is placed on aluminium-foil paper, puts into the baking oven of (185 ± 1) ℃, every l0 min sampling, observes sample variable color situation; Sample is cut into the small-particle that the length of side is 1 mm, packs in test tube, high 5 cm, are placed in 180 ℃ of constant temperature oil baths, measure the congo-red test paper variable color time.
Meanwhile, choose traditional Ca/Zn stablizer and test contrast.
Table 1 heat stability testing result
5, the present invention adopts dehydrochlorination experiment to investigate to the effect of PVC plastic degradation speed, can find out: the present invention can effectively reduce the degradation rate (as shown in Figure 1) of PVC.Experimental program is as follows:
By thermo-stabilizer, by the mixing that feeds intake of the formula rate of PVC 120 g, the present invention 30 g, mixed raw material is added on double roller plastic-making device, and at 180 ~ 200 ℃, mixing 5 min are in blocks.1 g materialses, be cut into the small-particle that the length of side is 1mm, be placed in the test tube of the logical people's nitrogen of constant speed, constant temperature oil bath temperature is (190 ± 1) ℃, the KC1 solution of usining absorbs as cuvette the HC gas that PVC thermal destruction removes, and measures the pH value of cuvette with E-201-C type thunder magnetic pH combined electrode and PHS-2F type digital pH meter on time.
6, preparation method of the present invention is simple, practical.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 is the de-HCl curves of PVC plastics of the present invention.
Embodiment
embodiment 1efficient, an environment-friendly polyvinyl chloride thermo-stabilizer, this stablizer is made by following quality (kg) component: 50 parts of Ca/Zn inorganic compounding soap salt, 2 parts of hydrotalcites, 1 part of phosphorous acid vinegar, 10 parts of beta-diketons, 1 part, paraffin.
Wherein: Ca/Zn inorganic compounding soap salt refers to when 25mL lipid acid is slowly warming up to 55 ~ 65 ℃ under at the uniform velocity stirring, add 4 g Glacial acetic acid, the 1.5 g vitriol oils, and to start to drip mass concentration be 20% hydrogen peroxide 10mL, 1 h dropwises, and in temperature, be to continue stirring reaction 3 h under the condition of 55 ~ 65 ℃, generate epoxyoleic acid; Epoxyoleic acid washes with water to neutrality, carries out vacuum hydro-extraction in vacuum tightness under the condition that is 0.1MPa, obtains the epoxyoleic acid that dewaters; After dehydration epoxyoleic acid is heated to 70 ~ 80 ℃, add 5.6g calcium hydroxide, 14.4 g zinc oxide, 1g strongly acidic cation-exchange, stir and get final product.
Paraffin refers to that molecular weight is the low molecular weight polyethylene wax of 1500-25000.
This is efficient, the preparation method of environment-friendly polyvinyl chloride thermo-stabilizer refers to: first by proportioning, weigh, then in Ca/Zn inorganic compounding soap salt, add successively hydrotalcite, phosphorous acid vinegar, beta-diketon, paraffin to react, reacted rear filtration, obtain complex Ca/Zn stablizer crude product, this complex Ca/Zn stablizer crude product is section according to a conventional method after being dried to constant weight under the condition of 25 ~ 35 ℃ in temperature, obtains calcium-zinc composite stabilizing agent product.
embodiment 2efficient, an environment-friendly polyvinyl chloride thermo-stabilizer, this stablizer is made by following quality (kg) component: 80 parts of Ca/Zn inorganic compounding soap salt, 14 parts of hydrotalcites, 9 parts of phosphorous acid vinegar, 20 parts of beta-diketons, 7 parts, paraffin.
Wherein: Ca/Zn inorganic compounding soap salt refers to when 150mL lipid acid is slowly warming up to 55 ~ 65 ℃ under at the uniform velocity stirring, add 20 g Glacial acetic acid, the 7.5 g vitriol oils, and to start to drip mass concentration be 30% hydrogen peroxide 45 mL, 1 h dropwises, and in temperature, be to continue stirring reaction 3 h under the condition of 55 ~ 65 ℃, generate epoxyoleic acid; Epoxyoleic acid washes with water to neutrality, carries out vacuum hydro-extraction in vacuum tightness under the condition that is 0.2MPa, obtains the epoxyoleic acid that dewaters; After dehydration epoxyoleic acid is heated to 70 ~ 80 ℃, add 28g calcium hydroxide, 72 g zinc oxide, 5g strongly acidic cation-exchange, stir and get final product.
Paraffin is same
embodiment 1.
This is efficient, the preparation method of environment-friendly polyvinyl chloride thermo-stabilizer is same
embodiment 1.
embodiment 3efficient, an environment-friendly polyvinyl chloride thermo-stabilizer, this stablizer is made by following quality (kg) component: 60 parts of Ca/Zn inorganic compounding soap salt, 6 parts of hydrotalcites, 3 parts of phosphorous acid vinegar, 12 parts of beta-diketons, 2 parts, paraffin.
Wherein: Ca/Zn inorganic compounding soap salt refers to when 50mL lipid acid is slowly warming up to 55 ~ 65 ℃ under at the uniform velocity stirring, add 8 g Glacial acetic acid, the 3 g vitriol oils, and to start to drip mass concentration be 22.5% hydrogen peroxide 19 mL, 1 h dropwises, and in temperature, be to continue stirring reaction 3 h under the condition of 55 ~ 65 ℃, generate epoxyoleic acid; Epoxyoleic acid washes with water to neutrality, carries out vacuum hydro-extraction in vacuum tightness under the condition that is 0.15MPa, obtains the epoxyoleic acid that dewaters; After dehydration epoxyoleic acid is heated to 70 ~ 80 ℃, add 10.9g calcium hydroxide, 28.8 g zinc oxide, 3g strongly acidic cation-exchange, stir and get final product.
Paraffin is same
embodiment 1.
This is efficient, the preparation method of environment-friendly polyvinyl chloride thermo-stabilizer is same
embodiment 1.
embodiment 4efficient, an environment-friendly polyvinyl chloride thermo-stabilizer, this stablizer is made by following quality (kg) component: 70 parts of Ca/Zn inorganic compounding soap salt, 10 parts of hydrotalcites, 7 parts of phosphorous acid vinegar, 17 parts of beta-diketons, 5 parts, paraffin.
Wherein: Ca/Zn inorganic compounding soap salt refers to when 100mL lipid acid is slowly warming up to 55 ~ 65 ℃ under at the uniform velocity stirring, add 16 g Glacial acetic acid, the 6 g vitriol oils, and to start to drip mass concentration be 27.5% hydrogen peroxide 36 mL, 1 h dropwises, and in temperature, be to continue stirring reaction 3 h under the condition of 55 ~ 65 ℃, generate epoxyoleic acid; Epoxyoleic acid washes with water to neutrality, carries out vacuum hydro-extraction in vacuum tightness under the condition that is 0.1MPa, obtains the epoxyoleic acid that dewaters; After dehydration epoxyoleic acid is heated to 70 ~ 80 ℃, add 22.2g calcium hydroxide, 57.6 g zinc oxide, 2g strongly acidic cation-exchange, stir and get final product.
Paraffin is same
embodiment 1.
This is efficient, the preparation method of environment-friendly polyvinyl chloride thermo-stabilizer is same
embodiment 1.
embodiment 5efficient, an environment-friendly polyvinyl chloride thermo-stabilizer, this stablizer is made by following quality (kg) component: 65 parts of Ca/Zn inorganic compounding soap salt, 8 parts of hydrotalcites, 5 parts of phosphorous acid vinegar, 15 parts of beta-diketons, 4 parts, paraffin.
Wherein: Ca/Zn inorganic compounding soap salt refers to when 80mL lipid acid is slowly warming up to 55 ~ 65 ℃ under at the uniform velocity stirring, add 12 g Glacial acetic acid, the 4.5 g vitriol oils, and to start to drip mass concentration be 25% hydrogen peroxide 28 mL, 1 h dropwises, and in temperature, be to continue stirring reaction 3 h under the condition of 55 ~ 65 ℃, generate epoxyoleic acid; Epoxyoleic acid washes with water to neutrality, carries out vacuum hydro-extraction in vacuum tightness under the condition that is 0.2MPa, obtains the epoxyoleic acid that dewaters; After dehydration epoxyoleic acid is heated to 70 ~ 80 ℃, add 16.3g calcium hydroxide, 43.2g zinc oxide, 4g strongly acidic cation-exchange, stir and get final product.
Paraffin is same
embodiment 1.
This is efficient, the preparation method of environment-friendly polyvinyl chloride thermo-stabilizer is same
embodiment 1.
Above-mentioned
embodiment 1 ~ 5efficient, the application of environment-friendly polyvinyl chloride thermo-stabilizer in preparing polrvinyl chloride product of gained, the add-on of this polychloroethylene heat stabilizer is 2% ~ 11% of polyvinyl chloride quality.
Claims (5)
1. efficient, an environment-friendly polyvinyl chloride thermo-stabilizer, is characterized in that: this stablizer is assigned to make by following quality group: 50 ~ 80 parts of Ca/Zn inorganic compounding soap salt, 2 ~ 14 parts of hydrotalcites, 1 ~ 9 part, phosphorous acid, 10 ~ 20 parts of beta-diketons, 1 ~ 7 part, paraffin.
2. a kind of efficient, environment-friendly polyvinyl chloride thermo-stabilizer as claimed in claim 1, it is characterized in that: described Ca/Zn inorganic compounding soap salt refers to when 25 ~ 150mL lipid acid is slowly warming up to 55 ~ 65 ℃ under at the uniform velocity stirring, add 4 ~ 20 g Glacial acetic acid, 1.5 ~ 7.5 g vitriol oils, and to start to drip mass concentration be 20% ~ 30% hydrogen peroxide 10 ~ 45 mL, 1 h dropwises, and in temperature, be to continue stirring reaction 3 h under the condition of 55 ~ 65 ℃, generate epoxyoleic acid; Described epoxyoleic acid washes with water to neutrality, carries out vacuum hydro-extraction in vacuum tightness under the condition that is 0.1 ~ 0.2MPa, obtains the epoxyoleic acid that dewaters; After described dehydration epoxyoleic acid is heated to 70 ~ 80 ℃, add 5.6 ~ 28g calcium hydroxide, 14.4 ~ 72 g zinc oxide, 1 ~ 5g strongly acidic cation-exchange, stir and get final product.
3. a kind of efficient, environment-friendly polyvinyl chloride thermo-stabilizer as claimed in claim 1, is characterized in that: described paraffin refers to that molecular weight is the low molecular weight polyethylene wax of 1500-25000.
4. the preparation method of a kind of efficient, environment-friendly polyvinyl chloride thermo-stabilizer as claimed in claim 1, it is characterized in that: first by proportioning, weigh, then in Ca/Zn inorganic compounding soap salt, add successively hydrotalcite, phosphorous acid vinegar, beta-diketon, paraffin to react, reacted rear filtration, obtain complex Ca/Zn stablizer crude product, this complex Ca/Zn stablizer crude product is section according to a conventional method after being dried to constant weight under the condition of 25 ~ 35 ℃ in temperature, obtains calcium-zinc composite stabilizing agent product.
5. a kind of efficient, the application of environment-friendly polyvinyl chloride thermo-stabilizer in preparing polrvinyl chloride product as claimed in claim 1, is characterized in that: the add-on of this polychloroethylene heat stabilizer is 2% ~ 11% of polyvinyl chloride quality.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199141A (en) * | 2015-09-15 | 2015-12-30 | 广州盈塑新材料科技有限公司 | One-step novel environment-friendly high-transparency flaky calcium-zinc heat stabilizer and preparation method thereof |
| CN106478990A (en) * | 2016-09-26 | 2017-03-08 | 深圳市志海实业股份有限公司 | A kind of novel melting one-step method prepares hydroxy fatty acid calcium zinc PVC stabilizer |
| CN107189258A (en) * | 2017-06-15 | 2017-09-22 | 苏州莱特复合材料有限公司 | A kind of preparation method of metal-based compound polychloroethylene heat stabilizer |
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| CN101031676A (en) * | 2004-09-29 | 2007-09-05 | 钟渊化学工业株式会社 | Polyvinyl chloride fiber reduced in initial coloration |
| US20070270532A1 (en) * | 2004-09-30 | 2007-11-22 | Kaneka Corporation | Polyvinyl Chloride Fiber and Process for Production Thereof |
| CN101735481A (en) * | 2010-01-06 | 2010-06-16 | 上海浩缘环保材料有限公司 | Organic calcium-zinc soap lye stabilizing agent |
| CN102492236A (en) * | 2011-11-22 | 2012-06-13 | 山东瑞丰高分子材料股份有限公司 | Novel high-efficiency calcium-zinc stabilizer applied for PVC (polyvinyl chloride) section bars and preparation method thereof |
| CN102504340A (en) * | 2011-11-04 | 2012-06-20 | 安徽师范大学 | Nontoxic calcium and zinc thermal stabilizer |
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2013
- 2013-12-11 CN CN201310665356.2A patent/CN103694599A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101031676A (en) * | 2004-09-29 | 2007-09-05 | 钟渊化学工业株式会社 | Polyvinyl chloride fiber reduced in initial coloration |
| US20070270532A1 (en) * | 2004-09-30 | 2007-11-22 | Kaneka Corporation | Polyvinyl Chloride Fiber and Process for Production Thereof |
| CN101735481A (en) * | 2010-01-06 | 2010-06-16 | 上海浩缘环保材料有限公司 | Organic calcium-zinc soap lye stabilizing agent |
| CN102504340A (en) * | 2011-11-04 | 2012-06-20 | 安徽师范大学 | Nontoxic calcium and zinc thermal stabilizer |
| CN102492236A (en) * | 2011-11-22 | 2012-06-13 | 山东瑞丰高分子材料股份有限公司 | Novel high-efficiency calcium-zinc stabilizer applied for PVC (polyvinyl chloride) section bars and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199141A (en) * | 2015-09-15 | 2015-12-30 | 广州盈塑新材料科技有限公司 | One-step novel environment-friendly high-transparency flaky calcium-zinc heat stabilizer and preparation method thereof |
| CN106478990A (en) * | 2016-09-26 | 2017-03-08 | 深圳市志海实业股份有限公司 | A kind of novel melting one-step method prepares hydroxy fatty acid calcium zinc PVC stabilizer |
| CN107189258A (en) * | 2017-06-15 | 2017-09-22 | 苏州莱特复合材料有限公司 | A kind of preparation method of metal-based compound polychloroethylene heat stabilizer |
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Application publication date: 20140402 |