CN109651826A - A kind of chlorinated fatty acid methyl esters Environment-friendlyheat heat stabilizer - Google Patents
A kind of chlorinated fatty acid methyl esters Environment-friendlyheat heat stabilizer Download PDFInfo
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- CN109651826A CN109651826A CN201811554145.0A CN201811554145A CN109651826A CN 109651826 A CN109651826 A CN 109651826A CN 201811554145 A CN201811554145 A CN 201811554145A CN 109651826 A CN109651826 A CN 109651826A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
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- 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
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- 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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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The present invention relates to heat stabilizer technical fields, especially a kind of chlorinated fatty acid methyl esters Environment-friendlyheat heat stabilizer, it includes the raw material of following mass fraction, 60-80 parts of epoxide, 1-10 parts of glycerin ether, 1-10 parts of organic acid zinc, 1-5 parts of organic base, without 1-10 parts of phenol phosphite ester, 1-5 parts of beta-diketon, 0.5-2 parts of antioxidant, 0.05-0.5 parts of light stabilizer, 0.05-0.5 parts and 5-15 parts of environmentally friendly solvent oil of ultraviolet absorbing agent, the epoxidized soybean oil that the epoxide is 1:2:3 by mass ratio, epoxidized vegetable oil and epoxy methyl esters composition, the Environment-friendlyheat heat stabilizer and chlorinated fatty acid methyl esters compatibility are good, the thermal decomposition temperature and uvioresistant stability of chlorinated fatty acid methyl esters can be improved, it can also be obviously improved its initial stage heat resistance simultaneously, And the feature of environmental protection is good, is free of toxic heavy metal component, usability is strong, and preparation method is easy to operate, easy to industrialized production.
Description
Technical field
The present invention relates to heat stabilizer technical field, especially a kind of chlorinated fatty acid methyl esters Environment-friendlyheat heat stabilizer.
Background technique
Chlorinated fatty acid methyl esters is a kind of yellow transparent oily liquids, is to carry out ester exchange reaction by natural oil and alcohol
Afterwards, then carry out chlorination reaction generation one kind have higher molecular weight product, chlorinated fatty acid methyl esters is good with PVC intermiscibility,
Plasticization effect is excellent, is a kind of fire-resistant, nontoxic, environmentally friendly compound plasticizer, also suitable especially suitable for the use of exported product
For industries such as PVC fire retarding conveying band, CABLE MATERIALS, PVC rain boots, PVC hose, interior leather for automobiles, artificial leather and sealing joint strips.By
In the existing esters structure of the product, alternative tributyl citrate and the phthalic ester plasticizer with carcinogenicity are made
For environment-friendly plasticizer use.Simultaneously because it also contains chlorine element, the anti-flammability and electrical insulating property of product can be greatly improved, is one
The ideal compound plasticizer of novel environment friendly of kind.
Chlorinated fatty acid methyl esters is due to containing the unstable chlorine atom on a small amount of or micro tertiary carbon atom, when heated or daylight
When irradiation, such unstable chlorine atom voluntarily can be detached from carbochain with adjacent hydrogen atom simultaneously, release HCl, and HCl again can be into
The decomposition of one step promotion chlorinated fatty acid methyl esters.Therefore, color when the chlorinated fatty acid methyl esters product resting period is too long or heated
It can gradually deepen, influence its use.Domestic chlorinated fatty acid methyl esters raw materials used purity, chlorination process and equipment and state
There is a certain distance in outer compare, thus chlorinated fatty acid methyl esters thermal stability is poor, causes heat stabilizer additive amount larger,
The share that the expense of stabilizer accounts for chlorinated fatty acid methyl esters cost is higher.
Its thermal decomposition temperature is mainly improved by one pack system or compounding in the dedicated stabilizer of chlorinated fatty acid methyl esters at present
Degree, due to heat stabilizer kind difference when, chemical structure and the mechanism of action are also different, and the single heat of each composition is steady
Determining agent has its limitation, therefore the heat stabilizer of single component is difficult to fully meet requirements above.And when two kinds or two kinds with
When the substance of upper particular utility is used cooperatively, gross effect is greater than the summation of each effect when being used alone, and passes through composite type heat
The research and development of stabilizer obtain the product with synergistic effect, are more able to satisfy requirement of the people to stabilizer.
Meanwhile the deficiency that existing chlorinated fatty acid methyl esters stabilizer is high there are feature of environmental protection difference and price, actual use
In initial stage heat resistance it is poor.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of chlorinated fatty acid methyl esters Environment-friendlyheat heat stabilizer, uses this
The thermal decomposition temperature and uvioresistant stability of chlorinated fatty acid methyl esters can be improved in Environment-friendlyheat heat stabilizer, while can also obviously change
It is apt to its initial stage heat resistance.
The technical solution of the present invention is as follows: a kind of chlorinated fatty acid methyl esters Environment-friendlyheat heat stabilizer, it includes following quality point
Several raw materials: 60-80 parts of epoxide, 1-10 parts of glycerin ether, 1-10 parts of organic acid zinc, 1-5 parts of organic base, without phenol phosphorous acid
1-10 parts of ester, 1-5 parts of beta-diketon, 0.5-2 parts of antioxidant, 0.05-0.5 parts of light stabilizer, 0.05-0.5 parts of ultraviolet absorbing agent
With 5-15 parts of environmentally friendly solvent oil, wherein the epoxide is made of epoxidized soybean oil, epoxidized vegetable oil and epoxy methyl esters；Institute
The mass ratio for stating epoxidized soybean oil, epoxidized vegetable oil and epoxy methyl esters is 1:2:3.
Further, it includes the raw material of following mass fraction: 65 parts of epoxide, 5 parts of glycerin ether, organic acid zinc 5
Part, 4 parts of organic base, without 8 parts of phenol phosphite ester, 3 parts of beta-diketon, 1 part of antioxidant, 0.3 part of light stabilizer, ultraviolet absorbing agent
0.2 part and 8.5 parts of environmentally friendly solvent oil, wherein the epoxide is by epoxidized soybean oil, epoxidized vegetable oil and epoxy methyl esters group
At；The mass ratio of the epoxidized soybean oil, epoxidized vegetable oil and epoxy methyl esters is 1:2:3.
Further, the glycerin ether is ethylene glycol diglycidylether, propanetriol-diglycidyl-ether and dodecyl contracting
One of water glycerin ether or more than one mixtures mixed in any proportion.
Further, the organic acid zinc is in zinc oleate, zinc Isoocatanoate, zinc benzoate and p-tert-butyl benzoic acid zinc
The mixture that one or more mix in any proportion.
Further, the organic base is the organic compound containing amino, comprising: in triethanolamine, methylamine and ethamine
The mixtures that mix in any proportion of one or more.
Further, the no phenol phosphite ester is triisodecyl phosphite ester, phosphorous acid trilaurin and pentaerythrite
One of phosphite ester or more than one mixtures mixed in any proportion.
Further, the beta-diketon is 3- methylbutyryl benzoyl methane, dibenzoyl methane and stearoyl benzoyl
One of methane or more than one mixtures mixed in any proportion.
Further, the antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three
In [2.4- di-tert-butyl-phenyl] phosphite ester and four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol esters
The mixtures that mix in any proportion of one or more.
Further, the light stabilizer is light stabilizer 770.
Further, the ultraviolet absorbing agent is one of UV-531, UV-9 and UV-326 or more than one are pressed and appoint
The mixture of meaning ratio mixing.
Further, the environmentally friendly solvent oil be white oil, de- fragrant one of solvent naphtha and transformer oil or more than one
The mixture mixed in any proportion.
In the present invention, each component raw material can play the role of synergistic effect, specific as follows:
Organic acid zinc and organic base can effectively inhibit initial coloration and the degradation of PVC sample as main effect stabilizer,
The heat-stable time of PVC is significantly increased, extends PVC and starts to discharge the time of HCl.
Epoxide is organic auxiliary stabilizer, and epoxide and hcl reaction generate chlorinating alcohols, in organic acid
Under the catalytic action of zinc, replace unstable chlorine atom in PVC and the effect of playing stably, so that it is efficiently modified thermostabilization efficiency,
Simultaneously under the catalysis of zinc salt, epoxide can also effectively substituted allyl chlorine atom.
Antioxidant can effectively inhibit the thermal degradation and oxidative degradation of polymer, have protection well to make thermo-oxidative ageing
With；
Light stabilizer 770 is light stabilizer, quenching singlet oxygen and hydroperoxides can be resolved into inert matter,
Slow down photochemical reaction possibility, prevents or the process of delay light aging, the addition of antioxidant and light stabilizer can make chloro rouge
The thermal decomposition temperature of fatty acid methyl esters improves 15 DEG C or so.
No phenol phosphite ester is environmental protection without phenolic liquid phosphite antioxidant, and main function is hydroperoxide decomposition,
The step of generation and accumulation of hydroperoxides are high-molecular organic material degradation most criticals, when certain density hydroperoxides
After generation, free-radical oxidation reaction will be quickly propelled, therefore phosphite antioxidant is most important to the inhibition of aging, meanwhile,
Phosphite antioxidant has good color protective capability, and the processing temperature that can improve polymer can not only improve PVC system
The initial coloration and transparency of product keep the brightness and consistency of colour of product, have with hindered phenol antioxygen, light stabilizer etc.
Synergy.
Beta-diketon is the light stabilizer and heat stabilizer of a kind of important thermoplastic, and beta-diketone compounds have
Efficiently, the advantages that nontoxic and multi-functional, is reacted with PVC and is stablized by C-alkylation effect, with solid or liquid calcium and
Zinc heat stabilizer is used in combination, and the speed of stabilization reactions can be improved, so as to improve PVC initial coloration, transparency, long-time stability with
And the precipitation in process and " zinc burning ".
Glycerin ether is organic heat stabilizers, can significantly improve the thermal decomposition temperature of chlorinated fatty acid methyl esters.
Ultraviolet absorbing agent is a kind of light stabilizer, can absorb the ultraviolet part in sunlight and fluorescent light source, and in itself
It does not change again.
Environmentally friendly solvent oil can increase the compatibility of oiliness and aqueous components in same system as dispersing agent.
The present invention also provides the preparation method of above-mentioned Environment-friendlyheat heat stabilizer, this method specifically: weighs institute by mass fraction
Raw material is needed, is stirred being warming up to 60 DEG C -70 DEG C and opening agitating device in epoxides investment reaction kettle, then successively
Be added glycerin ether, organic acid zinc, organic base, without phenol phosphite ester, beta-diketon, antioxidant, light stabilizer, ultraviolet absorbing agent and
Environmentally friendly solvent oil, is down to room temperature under temperature constant state after mixing evenly to obtain the final product.
Environment-friendlyheat heat stabilizer of the invention is mixed with chlorinated fatty acid methyl esters when in use, by the stabilizer,
The dosage of middle stabilizer is the 1.0-5.0% of chlorinated fatty acid methyl esters dosage.
The invention has the benefit that
(1) Environment-friendlyheat heat stabilizer of the present invention and chlorinated fatty acid methyl esters compatibility are good, and chlorinated fatty acid methyl esters can be improved
Thermal decomposition temperature and uvioresistant stability, while its initial stage heat resistance can also be obviously improved；
(2) the Environment-friendlyheat heat stabilizer feature of environmental protection of the present invention is good, is free of toxic heavy metal component, usability is strong, has a wide range of application；
(3) preparation method of the invention is easy to operate, easy to industrialized production.
Specific embodiment
Embodiment 1
A kind of chlorinated fatty acid methyl esters Environment-friendlyheat heat stabilizer, the raw material including following mass fraction: epoxide 60
Part, 1 part of glycerin ether, 1 part of organic acid zinc, 1 part of organic base, without 1 part of phenol phosphite ester, 1 part of beta-diketon, 0.5 part of antioxidant, light are steady
Determine 5 parts of 0.05 part of agent, 0.05 part of ultraviolet absorbing agent and environmentally friendly solvent oil, wherein epoxide is 1:2:3's by mass ratio
Epoxidized soybean oil, epoxidized vegetable oil and epoxy methyl esters composition.
The glycerin ether is in ethylene glycol diglycidylether, propanetriol-diglycidyl-ether and lauryl diglycidyl ether
The mixtures that mix in any proportion of one or more.
The organic acid zinc is one of zinc oleate, zinc Isoocatanoate, zinc benzoate and p-tert-butyl benzoic acid zinc or one
Kind or more the mixture that mixes in any proportion.
The organic base is the organic compound containing amino, comprising: one of triethanolamine, methylamine and ethamine or one
Kind or more the mixture that mixes in any proportion.
The no phenol phosphite ester is in triisodecyl phosphite ester, phosphorous acid trilaurin and pentaerythritol phosphite
The mixtures that mix in any proportion of one or more.
The beta-diketon is one in 3- methylbutyryl benzoyl methane, dibenzoyl methane and stearoyl benzoyl methane
Kind or more than one mixtures mixed in any proportion.
The antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three [the tertiary fourths of 2.4- bis-
Base phenyl] one of phosphite ester and four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol esters or one
Kind or more the mixture that mixes in any proportion.
The light stabilizer is light stabilizer 770.
The ultraviolet absorbing agent is one of UV-531, UV-9 and UV-326 or more than one are mixed in any proportion
Mixture.
The environmentally friendly solvent oil be white oil, de- fragrant one of solvent naphtha and transformer oil or more than one in any proportion
Mixed mixture.
Environment-friendlyheat heat stabilizer of the invention is mixed with chlorinated fatty acid methyl esters when in use, by stabilizer, wherein surely
The dosage for determining agent is the 4.0% of chlorinated fatty acid methyl esters dosage.
Epoxides is put into reaction kettle the preparation method is as follows: weigh required raw material by mass fraction by Environment-friendlyheat heat stabilizer
In, be warming up to 65 DEG C and open agitating device and be stirred, then sequentially add glycerin ether, organic acid zinc, organic base, without phenol Asia
Phosphate, beta-diketon, antioxidant, light stabilizer, ultraviolet absorbing agent and environmentally friendly solvent oil, under temperature constant state after mixing evenly
It is down to room temperature to obtain the final product.
Embodiment 2
A kind of chlorinated fatty acid methyl esters Environment-friendlyheat heat stabilizer, the raw material including following mass fraction: epoxide 65
Part, 5 parts of glycerin ether, 5 parts of organic acid zinc, 4 parts of organic base, without 8 parts of phenol phosphite ester, 3 parts of beta-diketon, 1 part of antioxidant, light stablize
8.5 parts of 0.3 part of agent, 0.2 part of ultraviolet absorbing agent and environmentally friendly solvent oil.Wherein, the ring that epoxide is 1:2:3 by mass ratio
Oxygen soybean oil, epoxidized vegetable oil and epoxy methyl esters composition.
The glycerin ether is in ethylene glycol diglycidylether, propanetriol-diglycidyl-ether and lauryl diglycidyl ether
The mixtures that mix in any proportion of one or more.
The organic acid zinc is one of zinc oleate, zinc Isoocatanoate, zinc benzoate and p-tert-butyl benzoic acid zinc or one
Kind or more the mixture that mixes in any proportion.
The organic base is the organic compound containing amino, comprising: one of triethanolamine, methylamine and ethamine or one
Kind or more the mixture that mixes in any proportion.
The no phenol phosphite ester is in triisodecyl phosphite ester, phosphorous acid trilaurin and pentaerythritol phosphite
The mixtures that mix in any proportion of one or more.
The beta-diketon is one in 3- methylbutyryl benzoyl methane, dibenzoyl methane and stearoyl benzoyl methane
Kind or more than one mixtures mixed in any proportion.
The antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three [the tertiary fourths of 2.4- bis-
Base phenyl] one of phosphite ester and four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol esters or one
Kind or more the mixture that mixes in any proportion.
The light stabilizer is light stabilizer 770.
The ultraviolet absorbing agent is one of UV-531, UV-9 and UV-326 or more than one are mixed in any proportion
Mixture.
The environmentally friendly solvent oil be white oil, de- fragrant one of solvent naphtha and transformer oil or more than one in any proportion
Mixed mixture.
Environment-friendlyheat heat stabilizer of the invention is mixed with chlorinated fatty acid methyl esters when in use, by stabilizer, wherein surely
The dosage for determining agent is the 4.0% of chlorinated fatty acid methyl esters dosage.
The preparation method is the same as that of Example 1.
Embodiment 3
A kind of chlorinated fatty acid methyl esters Environment-friendlyheat heat stabilizer, the raw material including following mass fraction, epoxide 80
Part, 10 parts of glycerin ether, 10 parts of organic acid zinc, 5 parts of organic base, without 10 parts of phenol phosphite ester, 5 parts of beta-diketon, 2 parts of antioxidant, light
15 parts of 0.5 part of stabilizer, 0.5 part of ultraviolet absorbing agent and environmentally friendly solvent oil, wherein epoxide is 1:2:3 by mass ratio
Epoxidized soybean oil, epoxidized vegetable oil and epoxy methyl esters composition.
The glycerin ether is in ethylene glycol diglycidylether, propanetriol-diglycidyl-ether and lauryl diglycidyl ether
The mixtures that mix in any proportion of one or more.
The organic acid zinc is one of zinc oleate, zinc Isoocatanoate, zinc benzoate and p-tert-butyl benzoic acid zinc or one
Kind or more the mixture that mixes in any proportion.
The organic base is the organic compound containing amino, comprising: one of triethanolamine, methylamine and ethamine or one
Kind or more the mixture that mixes in any proportion.
The no phenol phosphite ester is in triisodecyl phosphite ester, phosphorous acid trilaurin and pentaerythritol phosphite
The mixtures that mix in any proportion of one or more.
The beta-diketon is one in 3- methylbutyryl benzoyl methane, dibenzoyl methane and stearoyl benzoyl methane
Kind or more than one mixtures mixed in any proportion.
The antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three [the tertiary fourths of 2.4- bis-
Base phenyl] one of phosphite ester and four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol esters or one
Kind or more the mixture that mixes in any proportion.
The light stabilizer is light stabilizer 770.
The ultraviolet absorbing agent is one of UV-531, UV-9 and UV-326 or more than one are mixed in any proportion
Mixture.
The environmentally friendly solvent oil be white oil, de- fragrant one of solvent naphtha and transformer oil or more than one in any proportion
Mixed mixture.
Environment-friendlyheat heat stabilizer of the invention is mixed with chlorinated fatty acid methyl esters when in use, by stabilizer, wherein surely
The dosage for determining agent is the 4.0% of chlorinated fatty acid methyl esters dosage.
The preparation method is the same as that of Example 1.
Embodiment 4
As a comparison by the stabilizer of stabilizer made from 1-3 of the embodiment of the present invention and different material and weight proportion, it surveys
It tries stabilizer and the later thermal stable temperature of chlorinated fatty acid methyl esters, 180 DEG C of heat-stable times and light stable time is added.
Comparative example 1: on the basis of the formula of embodiment 2, organic acid zinc is removed, other components are identical.
Comparative example 2: on the basis of the formula of embodiment 2, organic base is removed, other components are identical.
Comparative example 3: it on the basis of the formula of embodiment 2, removes without phenol phosphite ester, other components are identical.
Comparative example 4: on the basis of the formula of embodiment 2, beta-diketon is removed, other components are identical.
Comparative example 5: on the basis of the formula of embodiment 2, light stabilizer 770 is removed, other components are identical.
Comparative example 6: on the basis of the formula of embodiment 2, ultraviolet absorbing agent is removed, other components are identical.
Comparative example 7: on the basis of the formula of embodiment 2, antioxidant is free of, other components are identical.
Embodiment 1-3 is measured respectively according to the measuring method of chlorinated paraffin heat stability index in national standard HG/T3018-1988
The later thermal stable temperature and time of chlorinated fatty acid methyl esters is added with comparative example 1-7.Its thermal stable temperature, 180 DEG C of thermostabilizations
It is as follows that time and light stablize the test method of time:
The measuring method of thermal stable temperature: 1. weigh the chlorinated fatty acid methyl esters sample 2g mixed in test tube, on folder
The Congored test paper handled well, is stoppered with rubber stopper；2. oil bath heating starts to warm up after temperature reaches 95 DEG C of stabilizations, is put into examination
Pipe observes Congored test paper color change；3. temperature when test paper occurs light blue is denoted as thermal stable temperature.
The measuring method of heat-stable time: 1. weigh the chlorinated fatty acid methyl esters sample 2g mixed in test tube, on folder
Congored test paper is stoppered with rubber stopper；2. oil bath heating is put into the test tube equipped with sample, opens after temperature reaches 180 DEG C of stabilizations
Congored test paper discoloration is observed in beginning timing；3. time when test paper occurs light blue is denoted as heat-stable time.
Light stablizes the measurement of time: it takes 2g sample to be placed in test tube, is put into the ageing oven equipped with ultraviolet lamp and observes, 1h
Afterwards, it is observed 1 time every 5min, record color starts the time of variation, ageing oven temperature 50 C ± 2 DEG C, revolving speed 3r/min.
Acquired results are as shown in table 1:
1 heat stability testing result of table
| Grouping | With difference of the invention | Thermal stable temperature/DEG C | 180 DEG C of heat-stable time/min | Light stablizes time/min |
| Implement 1 | / | 153 | 46 | 266 |
| Implement 2 | / | 165 | 52 | 280 |
| Implement 3 | / | 161 | 50 | 275 |
| Comparative example 1 | Without organic acid zinc | 135 | 30 | 224 |
| Comparative example 2 | Without organic base | 131 | 25 | 220 |
| Comparative example 3 | Without no phenol phosphite ester | 143 | 31 | 215 |
| Comparative example 4 | Without beta-diketon | 136 | 40 | 252 |
| Comparative example 5 | Without light stabilizer 770 | 143 | 30 | 85 |
| Comparative example 6 | Without ultraviolet absorbing agent | 145 | 35 | 180 |
| Comparative example 7 | Without antioxidant | 138 | 35 | 230 |
As shown in Table 1, the thermal stable temperature of Environment-friendlyheat heat stabilizer made from present invention implementation 1 reaches 153 DEG C, 180 DEG C of heat
The stable time reaches 46min, and the light stable time reaches 266min, and the thermal stable temperature of Environment-friendlyheat heat stabilizer made from implementation 2 reaches
To 165 DEG C, 180 DEG C of heat-stable times reach 52min, and the light stable time reaches 280min, Environment-friendlyheat heat stabilizer made from implementation 3
Thermal stable temperature reach 161 DEG C, 180 DEG C of heat-stable times reach 50min, and light stablizes the time and reaches 275min, it is seen then that this hair
The thermal stable temperature highest of Environment-friendlyheat heat stabilizer made from bright embodiment 2,180 DEG C of heat-stable times and light stablize time longest；
In addition, the thermal stable temperature of Environment-friendlyheat heat stabilizer made from 1-3 of the embodiment of the present invention is higher, 180 DEG C of heat-stable times and light
It is longer to stablize the time；Organic acid zinc, organic base are removed in comparative example 1-7 respectively, is stablized without phenol phosphite ester, beta-diketon, light
After agent 770, Environment-friendlyheat heat stabilizer made from ultraviolet absorbing agent and antioxidant, thermal stable temperature is lower, when 180 DEG C of thermostabilizations
Between and light stablize the time it is shorter, it is seen then that through the invention in each component mutual cooperation, the thermostabilization of Environment-friendlyheat heat stabilizer can be made
Temperature increases, and 180 DEG C of heat-stable times and light stablize time increase, greatly improves the stability of chlorinated fatty acid methyl esters,
Its surcharge is improved, it is made to be more conducive to the application in PVC manufacture field.
Embodiment 5
According to atomic absorption spectrography (AAS) and gravimetry to chlorinated fatty acid methyl esters stabilizer of the invention into
Row Analysis of Heavy Metal, the results are shown in Table 2:
2 content of beary metal of table
As shown in Table 2, the chlorinated fatty acid methyl esters that prepared by the embodiment of the present invention 1, embodiment 2 and embodiment 3 is steady with environmental protection
Determine agent and do not contain harmful heavy metal, meets environmental requirements.
Embodiment 6
Add the chlorinated fatty acid methyl esters of stabilizer prepared by 4% embodiment of the present invention 1, embodiment 2 and embodiment 3
Its initial stage is resistance to compared with the chlorinated fatty acid methyl esters for 4% organotin of chlorinated fatty acid methyl esters and addition for being not added with any stabilizer
It is hot.Its test method: 1. paste 100 parts of resins, 70 parts of plasticizer, 2 parts of stabilizer stir evenly in the pasty state；2. will be stirred
Material scratch in release paper, toast 10min in 180 DEG C of baking oven, observe the color of sample.The results are shown in Table 3:
Table 3 adds the heat ageing effect of chloro resin acid acid methyl esters after different heat stabilizers
| Plasticizer | Heat ageing grade |
| Chlorinated fatty acid methyl esters | 7 |
| Add the chlorinated fatty acid methyl esters of 4% organotin | 3 |
| Add the chlorinated fatty acid methyl esters of 4% embodiment 1 | 2 |
| Add the chlorinated fatty acid methyl esters of 4% embodiment 2 | 1 |
| Add the chlorinated fatty acid methyl esters of 4% embodiment 3 | 2 |
Remarks: -1 grade of white；Light yellow -2 grades；- 3 grades of yellow；- 4 grades of buff；- 5 grades of brown color；- 6 grades of rufous；It is brown
- 7 grades of color；- 8 grades of black.
As shown in Table 3, the chloro after stabilizer prepared by the embodiment of the present invention 1, embodiment 2 and embodiment 3 is added
Fatty acid methyl ester heat ageing effect is good, can be obviously improved its initial stage heat resistance, and cost is cheap.
The above embodiments and description only illustrate the principle of the present invention and most preferred embodiment, is not departing from this
Under the premise of spirit and range, various changes and improvements may be made to the invention, these changes and improvements both fall within requirement and protect
In the scope of the invention of shield.
Claims (10)
1. a kind of chlorinated fatty acid methyl esters Environment-friendlyheat heat stabilizer, it is characterised in that: it includes the raw material of following mass fraction: ring
60-80 parts of oxygen compound, 1-10 parts of glycerin ether, 1-10 parts of organic acid zinc, 1-5 parts of organic base, without 1-10 parts of phenol phosphite ester, β-
1-5 parts of diketone, 0.5-2 parts of antioxidant, 0.05-0.5 parts of light stabilizer, 0.05-0.5 parts of ultraviolet absorbing agent and environmentally friendly solvent oil
5-15 parts, wherein the epoxide is made of epoxidized soybean oil, epoxidized vegetable oil and epoxy methyl esters；The epoxy soybean
The mass ratio of oil, epoxidized vegetable oil and epoxy methyl esters is 1:2:3.
2. a kind of chlorinated fatty acid methyl esters Environment-friendlyheat heat stabilizer according to claim 1, it is characterised in that: it include with
The raw material of lower mass fraction: 65 parts of epoxide, 5 parts of glycerin ether, 5 parts of organic acid zinc, 4 parts of organic base, without phenol phosphite ester 8
Part, 3 parts of beta-diketon, 8.5 parts of 1 part of antioxidant, 0.3 part of light stabilizer, 0.2 part of ultraviolet absorbing agent and environmentally friendly solvent oil, wherein
The epoxide is made of epoxidized soybean oil, epoxidized vegetable oil and epoxy methyl esters；The epoxidized soybean oil, epoxidized vegetable oil
Mass ratio with epoxy methyl esters is 1:2:3.
3. a kind of chlorinated fatty acid methyl esters Environment-friendlyheat heat stabilizer according to claim 2, it is characterised in that: the glycerol
Ether be one of ethylene glycol diglycidylether, propanetriol-diglycidyl-ether and lauryl diglycidyl ether or more than one
The mixture mixed in any proportion.
4. a kind of chlorinated fatty acid methyl esters Environment-friendlyheat heat stabilizer according to claim 2, it is characterised in that: described organic
Sour zinc be one of zinc oleate, zinc Isoocatanoate, zinc benzoate and p-tert-butyl benzoic acid zinc or more than one in any proportion
Mixed mixture.
5. a kind of chlorinated fatty acid methyl esters Environment-friendlyheat heat stabilizer according to claim 2, it is characterised in that: described organic
Alkali be the organic compound containing amino, comprising: one of triethanolamine, methylamine and ethamine or more than one in any proportion
Mixed mixture.
6. a kind of chlorinated fatty acid methyl esters Environment-friendlyheat heat stabilizer according to claim 2, it is characterised in that: the no phenol
Phosphite ester be one of triisodecyl phosphite ester, phosphorous acid trilaurin and pentaerythritol phosphite or more than one
The mixture mixed in any proportion, the light stabilizer are light stabilizer 770, and the ultraviolet absorbing agent is UV-531, UV-
One of 9 and UV-326 or more than one mixtures mixed in any proportion.
7. a kind of chlorinated fatty acid methyl esters Environment-friendlyheat heat stabilizer according to claim 2, it is characterised in that: the β-two
Ketone is one of 3- methylbutyryl benzoyl methane, dibenzoyl methane and stearoyl benzoyl methane or more than one are pressed and appoint
The mixture of meaning ratio mixing.
8. a kind of chlorinated fatty acid methyl esters Environment-friendlyheat heat stabilizer according to claim 2, it is characterised in that: the antioxygen
Agent is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three [2.4- di-tert-butyl-phenyl] phosphite esters
With one of four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol esters or more than one in any proportion
Mixed mixture.
9. a kind of chlorinated fatty acid methyl esters Environment-friendlyheat heat stabilizer according to claim 2, it is characterised in that: the environmental protection
Solvent naphtha is white oil, de- fragrant one of solvent naphtha and transformer oil or more than one mixtures mixed in any proportion.
10. a kind of chlorinated fatty acid methyl esters Environment-friendlyheat heat stabilizer according to claim 1, it is characterised in that: the ring
Epoxides is put into reaction kettle the following steps are included: weigh required raw material by mass fraction by the preparation method of thermal protection stabilizer
In, be warming up to 60 DEG C -70 DEG C and open agitating device and be stirred, then sequentially add glycerin ether, organic acid zinc, organic base,
Without phenol phosphite ester, beta-diketon, antioxidant, light stabilizer, ultraviolet absorbing agent and environmentally friendly solvent oil, stirred under temperature constant state
Room temperature, which is down to, after uniformly obtains Environment-friendlyheat heat stabilizer.
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| CN201811554145.0A CN109651826A (en) | 2018-12-19 | 2018-12-19 | A kind of chlorinated fatty acid methyl esters Environment-friendlyheat heat stabilizer |
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