CN104448604A - Plasticizing composite heat stabilizer and preparation method thereof - Google Patents

Plasticizing composite heat stabilizer and preparation method thereof Download PDF

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Publication number
CN104448604A
CN104448604A CN201410551922.1A CN201410551922A CN104448604A CN 104448604 A CN104448604 A CN 104448604A CN 201410551922 A CN201410551922 A CN 201410551922A CN 104448604 A CN104448604 A CN 104448604A
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China
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calcium
rare earth
quality
parts
composite thermal
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CN201410551922.1A
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孟平蕊
李良波
林家耀
贾子扬
崔鸿凕
王敏明
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University of Jinan
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University of Jinan
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    • 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
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • 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
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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  • 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

The invention discloses a plasticizing composite heat stabilizer and a preparation method thereof. The preparation method is characterized by comprising the following steps: adding 500-900 parts by mass of water, 100 parts by mass of acidified oil, 15-30 parts by mass of rare earth chloride, 2-10 parts by mass of zinc sulfate, 10-25 parts by mass of calcium chloride and 20-50 parts by mass of a saponifying agent into a reactor and carrying out ultrasonic saponification reaction to obtain an acidified oil rare earth/calcium/zinc composite heat stabilizer; returning the acidified oil rare earth/calcium/zinc composite heat stabilizer to the reactor, adding 30-60 parts by mass of hydrogen peroxide and carrying out ultrasonic oxidation reaction to obtain an epoxidized acidified oil rare earth/calcium/zinc composite heat stabilizer, namely, the plasticizing composite heat stabilizer. The stabilizer has dual functions of a plasticizer and a stabilizer, and has the advantages of good mutual compatibility with PVC, strong synergetic effect, good thermal stability, superior tensile strength and elongation at break to those of DOP, cheap and easily available raw materials and lower cost, and the process is simple and environmentally friendly.

Description

A kind of plasticity composite thermal stabilizer and preparation method thereof
Technical field
The invention belongs to polyvinyl chloride (PVC) plastics organic additive technical field, relate to a kind of plasticity composite thermal stabilizer and preparation method thereof.
Background technology
Recently, as the rare-earth stearate salt of PVC heat stabilizer because it is nontoxic, tasteless, the feature such as high stable efficiency and good processing characteristics is concerned.Rare-earth stearate is the important a member in stearic acid stablizer family, has excellent stabilising effect to PVC.There is reinforcing effect between rare-earth stearate and different Metallic stearates, the one package stabilizer cooperation thermal stabilization be made up of rare-earth stearate salt, stearic acid calcium salt and stearic acid zinc salt is remarkable.
There are the following problems for the existing method preparing stearic acid one package stabilizer:
1, main raw material stearic acid is on the high side.Because domestic stearic acid source is with import plam oil for raw material is after shortening substantially, then carry out highly pressured hydrolysis, fatty acid, then carry out underpressure distillation and obtain;
2, one package stabilizer complicated process of preparation productive rate is low.First prepare rare-earth stearate salt, stearic acid calcium salt and stearic acid zinc salt respectively, and then be mixed in proportion obtained.Not only dust overall situation is polluted, and saponifying agent consumption is large, and water power consumption is large, and product is not easily separated, and productive rate is lower;
3, one package stabilizer is on the high side.Because main raw material stearic acid is on the high side, and complicated process of preparation, produced one package stabilizer just must be caused on the high side;
4, one package stabilizer thermostable effect is not good.Because the one package stabilizer particle diameter of common mixing is large, mixing is uneven, and poor with the mutual compatibility of polyvinyl chloride (PVC) RESINS, synergistic effect is undesirable.
Summary of the invention
The object of the invention is to overcome existing one package stabilizer and produce the deficiency existed, the one package stabilizer preparation method that a kind of excellent property has plasticity is provided.Adopt vegetable acid carburetion to make main raw material(s), there is cheaper starting materials and be easy to get; Three kinds of soaps synthesize acquisition composite thermal stabilizer by different ratios, work simplification simultaneously, and production cost is lower has plasticising and thermally-stabilised dual-use function.
The present invention is achieved by the following technical solutions:
In reactor, add water 500 ~ 900 quality divide, unlatching ultrasonic oscillator (50 ~ 100KHz, 100 ~ 500w), and electric mixer, limit is stirredwhile add 100 quality to divide acidification oil, rare earth chloride 15 ~ 30 quality is divided, zinc sulfate 2 ~ 10 quality is divided, calcium chloride 10 ~ 25 quality is divided, slowly add that saponifying agent 20 ~ 50 quality divides 70 ~ 90%, 50 ~ 90 0c, reaction 10 ~ 30min, adds remaining saponifying agent in 10 ~ 30min, continue reaction 10 ~ 30min, generate white precipitate, by reactant cooling, press filtration, obtain white or light yellow solid powder, vacuum drying oven is dry, obtains acidification oil rare earth // calcium // zinc salt composite thermal stabilizer.Again acidification oil rare earth/calcium // zinc salt composite thermal stabilizer is joined in reactor, limit stir just add hydrogen peroxide that 30 ~ 60 quality divide ultrasonic wave (50 ~ 100KHz, 100 ~ 500w) under vibration, 40 ~ 80 0c, reaction 0.5 ~ 2h, obtains white or light yellow solid powder, and vacuum drying oven is dry, both obtains epoxidation acidification oil rare earth // calcium // zinc salt composite thermal stabilizer, and is plasticity composite thermal stabilizer.
Described acidification oil is selected from one of following: eicosanoic acid carburetion, maizenic acid carburetion, rapic acid carburetion, soybean acidified oil, sunflower acidification oil, cotton acidification oil, palmitinic acid carburetion, flaxseed acidification oil;
Described rare-earth salts is: Lanthanum trichloride (La 2o 3/ REO is not less than 99.9), lanthanum concentrate rare earth chloride (La 2o 3/ TREO>=40 ~ 60);
Described calcium salt is: calcium chloride, calcium oxide;
Described zinc salt is: zinc sulfate, zinc oxide, zinc oxide;
Described saponifying agent is one of following: sodium hydroxide, potassium hydroxide;
Described hydrogen peroxide is the aqueous solution containing hydrogen peroxide 50%.
The invention has the beneficial effects as follows:
1, plasticity composite thermal stabilizer preparation method of the present invention, the deficiency that the main raw material stearic acid of existing one package stabilizer is on the high side can be made up, oil expression tankage acidification oil is used to substitute stearic acid, oil expression tankage are turned waste into wealth, not only reduce production cost, also improve the added value of oil expression tankage acidification oil, economic and social benefit is remarkable;
2, plasticity composite thermal stabilizer preparation method of the present invention, under ultra-sonic oscillation, adopt the novel process that three kinds of acidification oil soap is prepared in proportion simultaneously, compared with the common decomposite technique of respective duplication of production, not only simple process, the cycle, fugitive rate was high, the more important thing is that product is easily separated, aftertreatment is simple, and the few productive rate of product loss is high;
3, plasticity composite thermal stabilizer preparation method of the present invention, its equipment configuration does not need to do any repacking, laboratory or industrially all easily to realize.Following advantage is had: (1) does not need remix, simplifies experimental installation and operation, and staff it also avoid the harm that dust pollution brings compared with the common decomposite technique of respective duplication of production.(2) under sonic oscillation, the consumption of two step saponification method water and alkali obviously reduces and makes full use of, and can realize " atom economy " and change, hydrogen peroxide makees oxygenant, realizes zero release, meets green syt theory;
4, plasticity composite thermal stabilizer of the present invention is the nontoxic plasticity thermo-stabilizer of polyvinyl chloride.Reason is that the raw material acid carburetion that 100 quality are divided contains the lipid acid of about 70% and the grease of about 30%.Therefore epoxidation acidification oil rare earth // calcium // zinc salt stablizer that 100 quality are divided, be equivalent to containing the soap stablizer of about 2/3 and the epoxidation grease of about 1/3.In addition, under ultrasound condition, made one package stabilizer particle diameter is little, mixing evenly, good with polyvinyl chloride resin consistency, volatility is low, transport property is little, and its synergistic effect is strong, not only Heat stability is good, its plasticising performance can compare favourably with the good plasticizer DOP of PVC, and self is nontoxic.
Embodiment
Below in conjunction with embodiment, the present invention is described further, but protection scope of the present invention is not limited to embodiment.
embodiment one:
In reactor, add water 800 quality divide, open ultrasonic oscillator (50 kHz, 300w), and electric mixer, limit is stirredwhile add 100 quality to divide soybean acidified oil, rare earth chloride 25 quality is divided, zinc chloride 5 quality is divided, calcium chloride 18 quality is divided, slowly add that sodium hydroxide 30 quality divides 80%, 60 0c, reaction 30min, adds remaining sodium hydroxide in 15min, continue reaction 30min, generate white precipitate, by reactant cooling, press filtration, obtain white or light yellow solid powder, vacuum drying oven is dry, obtains soybean acidified oil rare earth/calcium // zinc salt composite thermal stabilizer.Again soybean acidified oil rare earth/calcium // zinc salt composite thermal stabilizer is joined in reactor, limit stir just add hydrogen peroxide that 50 quality divide ultrasonic wave ((50 ~ 100KHz, 100 ~ 500w) under vibration, 50 0c, reaction 1h, obtains white or light yellow solid powder, and vacuum drying oven is dry, obtains epoxidation soybean acidified oil rare earth // calcium // zinc salt composite thermal stabilizer, is plasticity composite thermal stabilizer, productive rate 95%, oxirane value 4.50%, median size 165nm.5 parts of these one package stabilizers are added, 180 at 100 parts of polyvinyl chloride resins 0it is 36min. that C congo red method measures its thermostability.Add 10 parts of these one package stabilizers at 100 parts of polyvinyl chloride resins, prepare material sample, test tensile strength is: 13.5 Mpa, and elongation at break is 310%; Add 10 parts of DOP softening agent at 100 parts of polyvinyl chloride resins, prepare material sample, test tensile strength is: 14.6 Mpa, elongation at break 320%.
embodiment two:
In reactor, add water 600 quality divide, open ultrasonic oscillator (100 kHz, 100w), and electric mixer, limit is stirredwhile add 100 quality to divide rapic acid carburetion, rare earth chloride 25 quality is divided, zinc sulfate 11 quality is divided, calcium chloride 18 quality is divided, slowly add that sodium hydroxide 30 quality divides 80%, 60 0c, reaction 20min, adds remaining sodium hydroxide in 15min, continue reaction 20min, generate white precipitate, by reactant cooling, press filtration, obtain white or light yellow solid powder, vacuum drying oven is dry, obtains rapic acid carburetion rare earth/calcium // zinc salt composite thermal stabilizer.Again rapic acid carburetion rare earth/calcium // zinc salt composite thermal stabilizer is joined in reactor, limit stir just add hydrogen peroxide that 50 quality divide ultrasonic wave ((50 ~ 100KHz, 100 ~ 500w) under vibration, 50 0c, reaction 1h, obtains white or light yellow solid powder, and vacuum drying oven is dry, obtains epoxidation rapic acid carburetion rare earth // calcium // zinc salt composite thermal stabilizer, is plasticity composite thermal stabilizer, productive rate 96%, oxirane value 3.14%, median size 160nm.5 parts of these one package stabilizers are added, 180 at 100 parts of polyvinyl chloride resins 0it is 40min. that C congo red method measures its thermostability.Add 10 parts of these one package stabilizers at 100 parts of polyvinyl chloride resins, prepare material sample, test tensile strength is: 16 Mpa, elongation at break 300%; Add 10 parts of DOP softening agent at 100 parts of polyvinyl chloride resins, prepare material sample, test tensile strength is: 14.6 Mpa, elongation at break 320%.
embodiment three:
In reactor, add water 800 quality divide, open ultrasonic oscillator (100 kHz, 200w), and electric mixer, limit is stirredwhile add 100 quality point cottonseed acid carburetion, lanthanum concentrate rare earth chloride 55 quality is divided, zinc oxide 6 quality is divided, calcium chloride 6 quality is divided, slowly add that sodium hydroxide 30 quality divides 80%, 80 0c, reaction 15min, adds remaining sodium hydroxide in 15min, continue reaction 10min, generate white precipitate, by reactant cooling, press filtration, obtain white or light yellow solid powder, vacuum drying oven is dry, obtains cottonseed acid carburetion rare earth/calcium // zinc salt composite thermal stabilizer.The cottonseed acid carburetion rare earth/calcium // zinc salt composite thermal stabilizer 100 quality divided again joins in reactor, limit stir just add hydrogen peroxide that 50 quality divide ultrasonic wave ((50 ~ 100KHz, 100 ~ 500w) under vibration, 50 0c, reaction 1h, obtain white or light yellow solid powder, vacuum drying oven is dry, obtains epoxidation cottonseed acid carburetion rare earth // calcium // zinc salt composite thermal stabilizer, is plasticity composite thermal stabilizer, productive rate 92%, oxirane value 3.36%, median size 162nm.5 parts of these one package stabilizers are added, 180 at polyvinyl chloride resin 0it is 39min. that C congo red method measures its thermostability.Add 10 parts of these one package stabilizers at 100 parts of polyvinyl chloride resins, prepare material sample, test tensile strength is: 15 Mpa, elongation at break 322%; Add 10 parts of DOP softening agent at 100 parts of polyvinyl chloride resins, prepare material sample, test tensile strength is: 14.6 Mpa, elongation at break 320%.
embodiment four:
In reactor, add water 600 quality divide, open ultrasonic oscillator (50 kHz, 300w), and electric mixer, limit is stirredwhile add 100 quality to divide maizenic acid carburetion, lanthanum concentrate rare earth chloride 55 quality is divided, zinc oxide 7 quality is divided, calcium oxide 6 quality is divided, slowly add that sodium hydroxide 30 quality divides 80%, 80 0c, reacts 10 min, adds remaining sodium hydroxide in 15min, continue reaction 15min, generate white precipitate, by reactant cooling, press filtration, obtain white or light yellow solid powder, vacuum drying oven is dry, obtains maizenic acid carburetion rare earth/calcium // zinc salt composite thermal stabilizer.Again maizenic acid carburetion rare earth/calcium // zinc salt composite thermal stabilizer is joined in reactor, limit stir just add hydrogen peroxide that 50 quality divide ultrasonic wave ((50 ~ 100KHz, 100 ~ 500w) under vibration, 50 0c, reaction 1h, obtain white or light yellow solid powder, vacuum drying oven is dry, obtains epoxidation maizenic acid carburetion rare earth // calcium // zinc salt composite thermal stabilizer, is plasticity composite thermal stabilizer, productive rate 94%, oxirane value 4.05%, median size 165nm.5 parts of these one package stabilizers are added, 180 at polyvinyl chloride resin 0it is 37min. that C congo red method measures its thermostability.Add 10 parts of these one package stabilizers at 100 parts of polyvinyl chloride resins, prepare material sample, test tensile strength is: 15.8Mpa, elongation at break 304%; Add 10 parts of DOP softening agent at 100 parts of polyvinyl chloride resins, prepare material sample, test tensile strength is: 14.6 Mpa, elongation at break 320%.

Claims (8)

1. the preparation method of plasticity composite thermal stabilizer, is characterised in that the method has following processing step:
(1) preparation of acidification oil rare earth // calcium // zinc salt composite thermal stabilizer: add water 600 ~ 1000 quality and divide in reactor, opens ultrasonic oscillator, and electric mixer, limit is stirreddivide while add acidification oil 100 quality, rare earth chloride 15 ~ 30 quality is divided, zinc sulfate 2 ~ 10 quality is divided, calcium chloride 10 ~ 25 quality is divided, slowly add that saponifying agent 20 ~ 50 quality divides 70 ~ 90%, 50 ~ 90 0c, reaction 10 ~ 30min, adds remaining sodium hydroxide in 10 ~ 30min, continue reaction 10 ~ 30min, generate white precipitate, by reactant cooling, press filtration, obtain white or light yellow solid powder, vacuum drying oven is dry, obtains acidification oil rare earth // calcium // zinc salt composite thermal stabilizer;
(2) preparation of epoxidation acidification oil rare earth // calcium // zinc salt composite thermal stabilizer: more above-mentioned acidification oil rare earth/calcium // zinc salt composite thermal stabilizer is joined in reactor, limit is stirred and is just added hydrogen peroxide that 30 ~ 60 quality divide under ultra-sonic oscillation, 40 ~ 80 0c, reaction 0.5 ~ 2h, obtains white or light yellow solid powder, and vacuum drying oven is dry, both obtains epoxidation acidification oil rare earth // calcium // zinc salt composite thermal stabilizer, and is plasticity composite thermal stabilizer.
2., according to right 1 requirement, described acidification oil is selected from one of following: eicosanoic acid carburetion, maizenic acid carburetion, rapic acid carburetion, soybean acidified oil, sunflower acidification oil, cotton acidification oil, coconut acid carburetion, palmitinic acid carburetion, Semen Lini oil.
3. rare-earth salts described in is: Lanthanum trichloride (La 2o 3/ REO is not less than 99.9), lanthanum concentrate rare earth chloride (La 2o 3/ TREO>=40 ~ 60).
4. according to right 1 requirement, described calcium salt is: calcium chloride, calcium oxide.
5. according to right 1 requirement, described zinc salt is: zinc sulfate, zinc oxide, zinc oxide.
6., according to right 1 requirement, described saponifying agent is one of following: sodium hydroxide, potassium hydroxide.
7. according to right 1 requirement, described hydrogen peroxide is: containing the aqueous solution of hydrogen peroxide 50%.
8., according to right 1 requirement, described ultrasonator is 50 ~100MHz, 100 ~ 500w, can common response device be inserted in ultrasonator; Also ultrasonic reaction still can directly be used.
CN201410551922.1A 2014-10-17 2014-10-17 Plasticizing composite heat stabilizer and preparation method thereof Pending CN104448604A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1277974A (en) * 2000-06-12 2000-12-27 郑德� Rare-earth multi-functional composite stabilizer for PVC and its processing method
CN1760277A (en) * 2005-11-04 2006-04-19 安徽建筑工业学院 Method for preparing processinga id for rare earths of a sort of polyvinyl chloride
CN102061042A (en) * 2010-11-23 2011-05-18 广东炜林纳功能材料有限公司 Rare earth thermal-stabilizing and plasticizing-promoting agent for PVC (polyvinyl chloride), composite additive of PVC and preparation methods thereof
CN102964748A (en) * 2012-12-20 2013-03-13 中国林业科学研究院林产化学工业研究所 Multi-effect grease-base PVC (polyvinyl chloride) heat stabilizer and preparation method thereof
CN103194005A (en) * 2013-04-01 2013-07-10 石河子大学 Method for preparing novel polyvinyl chloride (PVC) rare-earth heat stabilizer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1277974A (en) * 2000-06-12 2000-12-27 郑德� Rare-earth multi-functional composite stabilizer for PVC and its processing method
CN1760277A (en) * 2005-11-04 2006-04-19 安徽建筑工业学院 Method for preparing processinga id for rare earths of a sort of polyvinyl chloride
CN102061042A (en) * 2010-11-23 2011-05-18 广东炜林纳功能材料有限公司 Rare earth thermal-stabilizing and plasticizing-promoting agent for PVC (polyvinyl chloride), composite additive of PVC and preparation methods thereof
CN102964748A (en) * 2012-12-20 2013-03-13 中国林业科学研究院林产化学工业研究所 Multi-effect grease-base PVC (polyvinyl chloride) heat stabilizer and preparation method thereof
CN103194005A (en) * 2013-04-01 2013-07-10 石河子大学 Method for preparing novel polyvinyl chloride (PVC) rare-earth heat stabilizer

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

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