CN103194005A - Method for preparing novel polyvinyl chloride (PVC) rare-earth heat stabilizer - Google Patents

Method for preparing novel polyvinyl chloride (PVC) rare-earth heat stabilizer Download PDF

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CN103194005A
CN103194005A CN2013101090299A CN201310109029A CN103194005A CN 103194005 A CN103194005 A CN 103194005A CN 2013101090299 A CN2013101090299 A CN 2013101090299A CN 201310109029 A CN201310109029 A CN 201310109029A CN 103194005 A CN103194005 A CN 103194005A
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pvc
stabilizer
rare earth
lanthanum
rare
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马彦青
张伟
魏忠
但建明
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Shihezi University
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Shihezi University
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Abstract

The invention discloses a method for preparing a polyvinyl chloride (PVC) rare-earth heat stabilizer. The rare-earth heat stabilizer is lanthanum ricinoleate, and the chemical molecular formula is La(ri)3, wherein La expresses lanthanum, and ri expresses a ricinoleate radical. The preparation method comprises the following steps of: mixing a ricinoleic acid with an ethanol solution of a soluble rare-earth inorganic salt, dropwise adding an ethanol solution of an alkali, filtering, evaporating the solvent, washing and drying. By adopting the heat stabilizer, the initial dyeing property and the long-term heat stability of PVC can be improved; particularly, the rare-earth heat stabilizer and a calcium-zinc heat stabilizer, pentaerythritol, beta-diketone and the like are well synergistic and can be used for improving the heat stability, impact strength and breaking elongation of the PVC when being used together; and the rare-earth heat stabilizer has an industrial application prospect.

Description

A kind of preparation method of novel PVC rare earth thermal stabilizer
Technical field
The present invention relates to technical field of polymer materials, relate in particular to a kind of preparation method of PVC rare earth thermal stabilizer.
Background technology
Polyvinyl chloride (PVC) is one of the world's five big resins for universal use, its goods have soft durometer easy-regulating, mechanical property height, corrosion-resistant, electrical insulating property good, the transparency is high, advantage such as inexpensive, is widely used in production fields such as industry, agricultural.But degraded and crosslinking reaction easily take place in extraneous factor under as the effect of heat, light, oxygen and power in the poor stability of PVC, cause processing and use difficulty, mechanical properties decrease.Because the singularity of PVC structure, there is textural defect in molecular chain, can deviate from HCl when being heated to 110 ℃, and the HCl that emits can accelerate the decomposition of PVC, has a strong impact on the performance of polyvinyl chloride resin.And the processing temperature of PVC is generally more than 160 ℃, for PVC is become goods, usually add thermo-stabilizer in the course of processing of PVC, with the resin composition synergistic heat stabilizing system is arranged, prevent PVC in the course of processing owing to the degraded that is subjected to the mechanical shearing effect and is heated and causes, improve the heat decomposition temperature of PVC, enlarge its range of application.
The present world commercial PVC thermo-stabilizer mainly contains lead salt stabilizer, metallic soap one package stabilizer, organotin stabilizer and rare-earth stabilizer four big classes.The world wide production maximum be still traditional lead salts stablizer and metallic soap one package stabilizer, China is also based on this two classes stablizer.Lead salt stabilizer is developed the earliest, excellent in stability, and insulating property are better, and price is lower, but initial coloring is arranged, and lacks oilness, and goods are opaque, not anti-sulphide staining.In addition, the toxicity of lead salts stablizer is bigger, easily generates dust, and HUMAN HEALTH is had great harm.The metallic soap class will be used usually, adds to separate out easily man-hour, and stabilization efficiency is low, lead soap, cadmium soap good stability in the metal soap thermal stabilizers, but poisonous; Calcium soap, barium soap initial stage poor heat stability, zinc soap initial stage better heat stability, but persistence is poor, and " zinc burning " phenomenon easily takes place.The organic tin stablizer has splendid thermostability and the remarkable transparency, but expensive, lacks competitiveness.So these stablizers are progressively limited or are banned use of.Current, developing and develop the friendly type stablizer of nontoxic, efficient, composite multi-functional, cost performance fine environment has become urgent subject in the PVC manufacture field, has important economy and social effect.The rare earth class thermo-stabilizer has excellent thermally-stabilised function, and the transparency and weathering resistance are good, and has characteristics such as " coupling " property of uniqueness, nontoxic, safety and sanitation.In addition, rare earth thermal stabilizer electrical insulating property excellence, stable storing, asepsis environment-protecting has high cost performance.
Summary of the invention
The object of the present invention is to provide a kind ofly at above-mentioned deficiency of the prior art, a kind of PVC thermo-stabilizer with superior heat-stability, environmental protection is provided.
The technical solution used in the present invention is: a kind of PVC rare earth is thermally-stabilised, it is characterized in that, described rare earth thermal stabilizer is the ricinolic acid lanthanum, and its chemical molecular formula is La (ri) 3, La represents lanthanum, ri represents the Viscotrol C acid group.
The consumption of described ricinolic acid lanthanum is the 2-5% of PVC quality.
Described ricinolic acid lanthanum can be mixed and made into the composite PVC thermo-stabilizer with one or more of calcium stearate zinc, tetramethylolmethane, beta-diketon.
The heat-staple raw material composition of described composite PVC is counted by weight: ricinolic acid lanthanum 25~80, calcium stearate 20~85, Zinic stearas 0~50, tetramethylolmethane 0~20, beta-diketon 0~20.
Another object of the present invention has provided a kind of preparation aspect of PVC rare earth thermal stabilizer: preparation process is: mix ricinolic acid and soluble ree inorganic salt ethanolic soln, drip the ethanolic soln of alkali then, filter, steam solvent, the ricinolic acid lanthanum that washing is dry.
The thermo-stabilizer benchmark test
Static stability is tested (congo red method): according to GB GB/T2917.1-2002 congo red method, in the static atmosphere under certain stablizing, measure the sample top blue time of congo-red test paper change and estimate its thermostability.Pack into after at first that thermo-stabilizer PVC is even according to certain mixed and formulate in the test tube of specification, sample 50mm height, the bottom of congo-red test paper places 200 ℃ constant temperature glycerol bath apart from specimen surface 25mm, and the time that the record congo-red test paper becomes indigo plant is heat-stable time.
The PVC material properties test
Shock strength test: PVC is mixed with various auxiliary agents according to a certain ratio, at 170 ℃ down with pair roller opening rubber mixing machines 5min that plasticates, using the vulcanizing press tablet forming, with reference to GB/T1043-19933 plastics freely-supported beam type impact experiment method, the specimen shock strength, test piece is tailored into the sample of single breach on omnipotent sampling machine, five samples of parallel testing are averaged.
Tensile strength test: PVC is mixed with various auxiliary agents according to a certain ratio, 170 ℃ down with pair roller opening rubber mixing machines 5min that plasticates, using the vulcanizing press tablet forming, with reference to GB/T1040-1992 plastic tensile test method, the specimen tensile property.On omnipotent sampling machine the dumbbell shape sample is tailored in test piece, five samples of parallel testing are averaged.
Embodiment 1: the synthetic and application of ricinolic acid lanthanum
Respectively lanthanum nitrate, sodium hydroxide and ricinolic acid are dissolved in ethanol, be made into the lanthanum nitrate ethanolic soln the sodium hydroxide ethanolic soln and the ricinolic acid ethanolic soln standby.There-necked flask in the lanthanum nitrate ethanolic soln and the ricinolic acid ethanolic soln that add, under 70 ℃ of constant temperatures, stir, begin the sodium hydroxide ethanolic soln that from dropping funnel, slowly adds, reaction.Solution filters, and steams ethanol at Rotary Evaporators then, gets thick solid, washes drying with water.
Use:
Experimental group 1: with PVC100g, ricinolic acid lanthanum 2g is after mixing.Get an amount of sample and pack into and formulate in the test tube of specification, the high 50mm of sample, the bottom of congo-red test paper places 200 ℃ constant temperature glycerol bath apart from specimen surface 25mm.
Experimental group 2: with PVC100g, lead salt 2g is after mixing.Get an amount of sample and pack into and formulate in the test tube of specification, the high 50mm of sample, the bottom of congo-red test paper places 200 ℃ constant temperature glycerol bath apart from specimen surface 25mm.
Experimental group 3: with PVC100g, organotin (218) 2g is after mixing.Get an amount of sample and pack into and formulate in the test tube of specification, the high 50mm of sample, the bottom of congo-red test paper places 200 ℃ constant temperature glycerol bath apart from specimen surface 25mm.
Test group 4: with PVC100g, Zinic stearas 2g is after mixing.Get an amount of sample and pack into and formulate in the test tube of specification, the high 50mm of sample, the bottom of congo-red test paper places 200 ℃ constant temperature glycerol bath apart from specimen surface 25mm.
Experimental group 5: with PVC100g, tetramethylolmethane 2g is after mixing.Get an amount of sample and pack into and formulate in the test tube of specification, the high 50mm of sample, the bottom of congo-red test paper places 200 ℃ constant temperature glycerol bath apart from specimen surface 25mm.
Experimental group 6: with PVC100g, beta-diketon 2g is after mixing.Get an amount of sample and pack into and formulate in the test tube of specification, the high 50mm of sample, the bottom of congo-red test paper places 200 ℃ constant temperature glycerol bath apart from specimen surface 25mm.
Control group: get an amount of blank PVC sample and pack into and formulate in the test tube of specification, the high 50mm of sample, the bottom of congo-red test paper places 200 ℃ constant temperature glycerol bath apart from specimen surface 25mm.
Survey the static heat steady time of each experimental group respectively.The result as shown in Table 1, the ricinolic acid lanthanum a little less than lead salt, and is higher than other conventional thermo-stabilizers to the thermostability of PVC, can be used as the PVC thermo-stabilizer.
Table 1 contains the various conventional thermo-stabilizer to the heat-stable time contrast of PVC
Figure BSA00000871710000021
Embodiment 2: PVC300g, described thermo-stabilizer 9g are evenly mixed, 170 ℃ down with pair roller opening rubber mixing machines 5min that plasticates, using the vulcanizing press tablet forming, according to the standard sample preparation, the evaluating material performance.
Comparative group 1: thermo-stabilizer is lead salt
Comparative group 2: thermo-stabilizer is organotin 218
Experimental group 1: thermo-stabilizer is the ricinolic acid lanthanum
Experimental group 2: thermo-stabilizer is: composite thermal stabilizer 1 (ricinolic acid lanthanum, calcium stearate, Zinic stearas and tetramethylolmethane were according to 30: 45: 15: 10 quality is than uniform mixture).
Experimental group 3: thermo-stabilizer is: composite thermal stabilizer 2 (ricinolic acid lanthanum, calcium stearate, Zinic stearas, tetramethylolmethane and beta-diketon were according to 30: 45: 15: 10: 7 quality is than uniform mixture).
The PVC performance of table 2 different stabilizers relatively
Table 2 is tensile strength, shock strength and the elongation at break results that add the PVC of different thermo-stabilizers, compare as can be seen lead salt and organotin 218, rare-earth stabilizer and rare earth composite stabilizer all have significant improvement to shock strength and the elongation at break to the PVC material, illustrate that rare earth composite stabilizer can effectively improve the mechanical property of PVC material.

Claims (7)

1. a rare earth PVC thermo-stabilizer is characterized in that, described rare earth is the ricinolic acid lanthanum, and chemical molecular formula is La (ri) 3,La represents lanthanum, and ri represents the Viscotrol C acid group.
2. according to the described a kind of rare earth PVC thermo-stabilizer of claim 1, it is characterized in that: the consumption of described ricinolic acid lanthanum is the 2-5% of PVC quality.
3. a kind of rare earth PVC thermo-stabilizer according to claim 1 is characterized in that: described ricinolic acid lanthanum can be mixed and made into the composite PVC thermo-stabilizer with one or more of calcium stearate zinc, tetramethylolmethane, beta-diketon.
4. require described a kind of rare earth PVC thermo-stabilizer according to right 3, it is characterized in that: the heat-staple raw material composition of described composite PVC is counted by weight: ricinolic acid lanthanum 25~80, calcium stearate 20~85, Zinic stearas 0~50, tetramethylolmethane 0~20, beta-diketon 0~20.
One kind prepare require as right 1 as described in a kind of preparation method of rare earth PVC thermo-stabilizer, it is characterized in that preparation process is: mix ricinolic acid and soluble ree inorganic salt ethanolic soln, drip the ethanolic soln of alkali then, filter, steam solvent, the ricinolic acid lanthanum that washing is dry.
6. according to the preparation method of the described a kind of rare earth PVC thermo-stabilizer of claim 5, it is characterized in that: described alkali is sodium hydroxide, potassium hydroxide or their combination.
7. according to the preparation method of the described a kind of rare earth PVC thermo-stabilizer of claim 5, it is characterized in that: described soluble ree inorganic salt refer to lanthanum nitrate or Lanthanum trichloride.
CN2013101090299A 2013-04-01 2013-04-01 Method for preparing novel polyvinyl chloride (PVC) rare-earth heat stabilizer Pending CN103194005A (en)

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103865195A (en) * 2014-03-10 2014-06-18 唐山师范学院 Composite thermal stabilizing agent for dark hard PVC (Polyvinyl Chloride) and preparation method thereof
CN103865196A (en) * 2014-03-12 2014-06-18 江西宏远化工有限公司 Compound rare-earth calcium zinc heat stabilizer as well as preparation method and use method thereof
CN104448604A (en) * 2014-10-17 2015-03-25 济南大学 Plasticizing composite heat stabilizer and preparation method thereof
CN105295218A (en) * 2015-11-18 2016-02-03 安徽华塑股份有限公司 Hydrotalcite and lanthanum ricinoleate composite environmental-protection stabilizer for PVC and preparation method thereof
CN106221077A (en) * 2016-08-31 2016-12-14 高亚莉 The anti-PVC material and preparation method thereof that fractures of environment-friendly type
CN106380741A (en) * 2016-09-22 2017-02-08 佛山市飞时达新材料科技有限公司 Method for manufacturing environmental-friendly PVC cable material
CN107540989A (en) * 2017-10-16 2018-01-05 天津城建大学 A kind of ternary nano rare-earth complex composite thermal stabilizer
CN107602922A (en) * 2017-08-07 2018-01-19 郑州庆宏塑胶科技有限公司 A kind of preparation method of itaconic acid bright-coloured composite thermal stabilizer
CN110330514A (en) * 2019-05-09 2019-10-15 包头稀土研究院 Rare earth ion-fragrance ketone complex, stabilizer and its preparation method and application
CN110358221A (en) * 2019-07-29 2019-10-22 唐山师范学院 PVC sorbic acid lanthanum composite thermal stabilizer
CN111533641A (en) * 2020-05-16 2020-08-14 内蒙古联丰稀土化工研究院有限公司 Preparation method of glycerin rare earth
CN114644777A (en) * 2022-04-20 2022-06-21 黄山佳宝新材料科技有限公司 Rare earth heat stabilizer for high-transparency PVC (polyvinyl chloride) product and preparation method thereof
CN114933882A (en) * 2022-06-14 2022-08-23 广东菊兰新型材料科技有限公司 Durable sealant with ultrahigh elongation, high adhesion and high toughness and preparation method thereof
CN115678182A (en) * 2022-11-14 2023-02-03 浙江中财管道科技股份有限公司 High-impact-resistance weather-resistant road cone and manufacturing method thereof

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CN101602863A (en) * 2009-06-22 2009-12-16 温州天盛塑料助剂有限公司 The environmental-friendly dust-free calcium-zinc composite heat stabilizer that is used for PVC processing

Patent Citations (1)

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CN101602863A (en) * 2009-06-22 2009-12-16 温州天盛塑料助剂有限公司 The environmental-friendly dust-free calcium-zinc composite heat stabilizer that is used for PVC processing

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103865195A (en) * 2014-03-10 2014-06-18 唐山师范学院 Composite thermal stabilizing agent for dark hard PVC (Polyvinyl Chloride) and preparation method thereof
CN103865195B (en) * 2014-03-10 2016-04-27 唐山师范学院 Dark hard PVC composite thermal stabilizer and preparation method thereof
CN103865196A (en) * 2014-03-12 2014-06-18 江西宏远化工有限公司 Compound rare-earth calcium zinc heat stabilizer as well as preparation method and use method thereof
CN104448604A (en) * 2014-10-17 2015-03-25 济南大学 Plasticizing composite heat stabilizer and preparation method thereof
CN105295218A (en) * 2015-11-18 2016-02-03 安徽华塑股份有限公司 Hydrotalcite and lanthanum ricinoleate composite environmental-protection stabilizer for PVC and preparation method thereof
CN106221077A (en) * 2016-08-31 2016-12-14 高亚莉 The anti-PVC material and preparation method thereof that fractures of environment-friendly type
CN106380741A (en) * 2016-09-22 2017-02-08 佛山市飞时达新材料科技有限公司 Method for manufacturing environmental-friendly PVC cable material
CN107602922A (en) * 2017-08-07 2018-01-19 郑州庆宏塑胶科技有限公司 A kind of preparation method of itaconic acid bright-coloured composite thermal stabilizer
CN107540989A (en) * 2017-10-16 2018-01-05 天津城建大学 A kind of ternary nano rare-earth complex composite thermal stabilizer
CN110330514A (en) * 2019-05-09 2019-10-15 包头稀土研究院 Rare earth ion-fragrance ketone complex, stabilizer and its preparation method and application
CN110358221A (en) * 2019-07-29 2019-10-22 唐山师范学院 PVC sorbic acid lanthanum composite thermal stabilizer
CN111533641A (en) * 2020-05-16 2020-08-14 内蒙古联丰稀土化工研究院有限公司 Preparation method of glycerin rare earth
CN114644777A (en) * 2022-04-20 2022-06-21 黄山佳宝新材料科技有限公司 Rare earth heat stabilizer for high-transparency PVC (polyvinyl chloride) product and preparation method thereof
CN114933882A (en) * 2022-06-14 2022-08-23 广东菊兰新型材料科技有限公司 Durable sealant with ultrahigh elongation, high adhesion and high toughness and preparation method thereof
CN115678182A (en) * 2022-11-14 2023-02-03 浙江中财管道科技股份有限公司 High-impact-resistance weather-resistant road cone and manufacturing method thereof

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Application publication date: 20130710