Polythiaether PVC co-stabilizers and preparation method and application
Technical field
The present invention relates to chemical technology field, more particularly to a kind of polythiaether PVC co-stabilizers and preparation method thereof with
Using.
Background technology
Polyvinyl chloride (PVC) is one of thermoplastic for being developed earliest in the world, and it is because with excellent acid and alkali-resistance
Property, wearability, electrical insulating property are good, flame retardancy, and mature production technology, low cost, the characteristics of be easier to machine-shaping, become only
Inferior to polyethylene, polyacrylic the third-largest synthetic resin.
However, PVC adds at high temperature man-hour, it may occur that eliminate disconnected and macromolecular the crosslinking of hydrogen chloride, key, and cause PVC
Generation degraded coloring, mechanical performance declines, therefore heat stabilizer must be used in processing PVC.
Through years development, a great variety of PVC heat stabilizer, by the difference of complicated components, one-component heat can be divided into
Stabilizer and the big class of composite thermal stabilizer two.One-component heat stabilizer mainly includes metal soap, lead heat stabilizer, has
Machine tin heat stabilizer, organic antimomy stabilizer, hydrotalcite heat stabilizer and without metal heat stabilizer.And by two kinds or two kinds with
It is mixed that upper one pack system heat stabilizer or the one pack system heat stabilizer by more than one and more than one co-stabilizers (auxiliary agent) are constituted
Mould assembly stabilizer is referred to as composite thermal stabilizer.Composite thermal stabilizer can be divided into following six big class because of the difference of its main effect component:Lead
Based composite heat stabilizer, zinc-base composite thermal stabilizer, cadmium based composite heat stabilizer, organotin based composite heat stabilizer, antimony base are answered
Close heat stabilizer and organic based composite heat stabilizer.Composite thermal stabilizer with the characteristics of its combination property balance, high performance-price ratio into
For the main body of commodity heat stabilizer.
At present, PVC heat stabilizer new product development is concentrated mainly on research and development and the compound thermal of new one pack system heat stabilizer
In the design of stabilizer.There is technology to disclose a kind of new latent mercaptan PVC heat stabilizer.This new heat stabilizer is not only
It is used alone and there is good thermal stability, and is greatly carried with the thermostable effect after Ca-Zn composite heat stabilizer compounding
It is high.Also technology discloses the method that dimercapto maleate PVC heat stabilizer is synthesized using maleic anhydride and mercaptoethanol,
So the dimercapto maleate of synthesis can be while keeps thermally-stabilised and the transparency with organo-tin het stabilizer compounding, drop
Low tin content, reduces cost.Also technology describes catechol and its derivative and compounds what is obtained with organic antimomy stabilizer
Antimony base compound stabilizer not only has good heat stabilizer, and improves the storage performance of heat stabilizer.Also technology
Disclose Cosan, mercaptan acid and organic antimomy stabilizer and be combined the antimony base compound stabilizer for obtaining and have preferable ultraviolet light steady
Qualitative energy and storage performance.
Have technology to describe that disulfide is obtained by isooctyl thioglycolate and sulfur reaction, as PVC co-stabilizers with
Organo-tin het stabilizer compounding use, can improve heat endurance.But the shortcoming of the preparation method of the technology is to generate in a large number
Violent in toxicity hydrogen sulfide.
The content of the invention
Based on this, it is necessary to for the problems referred to above, there is provided a kind of polythiaether PVC co-stabilizers and preparation method thereof with should
With.The preparation method of the present invention overcomes the shortcoming of existing preparation method using the oxidant of environment-friendly type.The present invention is also to many sulphur
Ether is studied as PVC co-stabilizers with Ca-Zn composite heat stabilizer, organic antimomy stabilizer compounding use.
Concrete technical scheme is as follows:
The invention discloses a kind of preparation method of polythiaether PVC co-stabilizers, the preparation method is comprised the following steps:
It is by the mixing of sulfhydryl compound, oxidant and reflux solvent, the mol ratio of the sulfhydryl compound, oxidant and reflux solvent
1~2:1:1~2, and the catalyst of the sulfhydryl compound weight 0.01%~3% is added, it is anti-at a temperature of 60~200 DEG C
After answering 1~10h, drying steams solvent, obtains final product;
The polythiaether PVC co-stabilizers have following structure shown in formula I:
R1—Sn—R2(I),
In formula I, S is element sulphur, and n is 1~6 integer;R1And R2It is identical or differ, R1And R2Selected from alkyl, R3OH、
R4-COOR5And R6-OOCR7;
R3、R4、R5、R6And R7Selected from alkyl, thiazolinyl, alkynyl, aryl, cycloalkyl, cycloalkenyl group;
The alkyl is alkyl, thiazolinyl, alkynyl, aryl, cycloalkyl or cycloalkenyl group.
Wherein in some embodiments, the sulfhydryl compound is 2 mercapto ethanol, 3- sulfydryl -1- propyl alcohol, 2- methyl -2-
In mercaptoethanol, 4- Mercaptobutanols, lauryl mercaptan, isooctyl thioglycolate and aliphatic acid mercapto ethyl ester at least one
Kind;The aliphatic acid mercapto ethyl ester is selected from sad mercapto ethyl ester, capric acid mercapto ethyl ester, laurate mercapto ethyl ester, cocinic acid mercapto
Base ethyl ester, palmitic acid mercapto ethyl ester, stearic acid mercapto ethyl ester, vegetable oil acid mercapto ethyl ester, arachidic acid mercapto ethyl ester;
The reflux solvent is the one kind in dimethylbenzene, toluene and hexamethylene;
The oxidant is at least one in hydrogen peroxide and the bromo- 5,5- DMHs of 1,3- bis-;
The catalyst is at least one in triethylamine, formamide and isobutyramide.
Wherein in some embodiments, the sulfhydryl compound is 2 mercapto ethanol, 3- sulfydryl -1- propyl alcohol, dodecyl
At least one in mercaptan, isooctyl thioglycolate and aliphatic acid mercapto ethyl ester;The aliphatic acid mercapto ethyl ester is selected from bay
Sour mercapto ethyl ester, cocinic acid mercapto ethyl ester, vegetable oil acid mercapto ethyl ester;
The reflux solvent is at least one in toluene and dimethylbenzene;
Described oxidant is hydrogen peroxide;
The catalyst is at least one in triethylamine and isobutyramide.
Above-mentioned sulfhydryl compound is more preferably 2 mercapto ethanol, isooctyl thioglycolate, laurate mercapto ethyl ester, vegetable oil
Sour mercapto ethyl ester.
Wherein in some embodiments, the consumption of the catalyst be the sulfhydryl compound weight 0.9%~
1.5%.
Wherein in some embodiments, the reaction temperature is 80~160 DEG C, and the reaction time is 1~3h.
Wherein in some embodiments, the polythiaether PVC co-stabilizers be 2,2- dihydroxy diethyl disulphides, diethyl
The different monooctyl ester disulfide of acid, tin dilaurate ethyl ester disulfide or two vegetable oil acid ethyl ester disulfides.
Invention additionally discloses a kind of preparation-obtained polythiaether PVC co-stabilizers of above-mentioned preparation method.
Invention additionally discloses above-mentioned polythiaether PVC co-stabilizers are warm with organo-tin het stabilizer compounding preparation increase PVC
Application in the composite thermal stabilizer of stability.
Invention additionally discloses above-mentioned polythiaether PVC co-stabilizers are preventing PVC zinc from burning with calcium zinc heat stabilizer compounding preparation
Application in the composite thermal stabilizer of phenomenon.
Invention additionally discloses above-mentioned polythiaether PVC co-stabilizers are to improve PVC purple with the preparation of organic antimomy stabilizer compounding
Application in the composite thermal stabilizer of outer photostability and storage stability.
The present invention provides a kind of new polythiaether PVC co-stabilizers and preparation method thereof, overcomes existing preparation method to produce
The shortcoming of the substantial amounts of violent in toxicity hydrogen sulfide of life, while the co-stabilizer is expanded hard transparent PVC product is applied to, with splendid
Compatibility, help stability, the transparency and ultraviolet light stability.The present invention is easily oxidized contracting using the mercapto groups of thiol molecule
Synthesis polythiaether, and then the molecular chain length of sulfhydryl compound is substantially increased, increased molecular mass so as to as co-stabilizer
When significantly improve with the compatibility of PVC molecules, with lubrication property in more preferable, be not easy to separate out in process.
The present invention compares the advantage of prior art and has the beneficial effect that:
(1) Optimization of preparation:Generation without violent in toxicity hydrogen sulfide, oxidation product is water, and reaction yield is high, uses
Solvent boiling point is higher, easily reclaims;
(2) good stability is helped:Polythiaether co-stabilizer synthesized by the present invention has preferable with organo-tin het stabilizer
Compatibility and synergy, are a kind of preferable auxiliary heat stabilizers, and can be prevented with the use of playing with calcium zinc heat stabilizer
The effect of " zinc burning ";
(3) greasy property is good:Polythiaether co-stabilizer synthesized by the present invention possesses larger molecular weight, with PVC molecules
Compatibility preferably, fabulous lubrication can be played, and be not easy to separate out in process;
(4) ultraviolet light stabilized performance is good:Polythiaether co-stabilizer synthesized by the present invention has preferable ultraviolet light stabilized
Performance.
Specific embodiment
To be best understood from the present invention, with reference to embodiment further detailed description is done to the present invention, but the present invention
Embodiment not limited to this.
Supplier or the preparation method for occurring raw material and equipment in embodiment is as follows:
The product that 2 mercapto ethanol is provided for China Petroleum & Chemical Co., Ltd. Maoming Branch, technical grade;
The product that 30% hydrogen peroxide is provided for Guangzhou Chemical Reagent Factory, analyzes pure;
The product that hexamethylene is provided for Guangzhou Chemical Reagent Factory, analyzes pure;
The product that triethylamine is provided for Chengdu Kingsoft chemical reagent Co., Ltd, analyzes pure;
The product that isobutyramide is provided for Hubei Ju Sheng Science and Technology Ltd.s, SILVER REAGENT;
The product that isooctyl thioglycolate is provided for Sanmenxia Aoke Chemical Industry Co., Ltd., technical grade;
The product that toluene is provided for Maoming Hao Jie chemical industry Co., Ltd, technical grade;
The product that dimethylbenzene is provided for Guangzhou Chemical Reagent Factory, analyzes pure;
The product that laurate is provided for Guangzhou Fu Rui Chemical Co., Ltd.s, technical grade;
The product that vegetable oil acid is provided for big western general chemistry (Sichuan) Co., Ltd of standing grain, technical grade;
The preparation method of laurate mercapto ethyl ester and vegetable oil acid mercapto ethyl ester:
Laurate or vegetable oil acid carry out esterification with mercaptoethanol respectively, wherein, laurate or vegetable oil acid can be by
Acid number calculates the amount of the material of its carboxyl, for calculation in the molar ratio, the carboxyl in laurate or vegetable oil acid and sulfydryl in raw material
The mol ratio of ethanol is 1:1.2, the catalyst p-methyl benzenesulfonic acid of reaction-ure mixture 1 ‰ is added, carry out ester in vacuum 50-70 DEG C
Change reaction, until the acid number of reactant liquor is less than 20mgKOH/g, be considered as esterification terminal, be filtrated to get laurate mercapto ethyl ester
Or vegetable oil acid mercapto ethyl ester.
Embodiment 1
A kind of preparation method of polythiaether PVC co-stabilizers, comprises the following steps:
In equipped with agitator, thermometer, the four-hole boiling flask of water cooling condensate liquid water knockout drum, 156.24g2- sulfydryls are added
(mol ratio between above-mentioned 2 mercapto ethanol, 30% hydrogen peroxide, toluene is 2 for ethanol, 30% hydrogen peroxide 113.4g, 185g toluene:
1:2), 1.6g catalyst of triethylamine, stirring reaction 1.5h at 80 DEG C, then distillation removes organic solvent and obtains 151.3g 2,
2- dihydroxy diethyl disulphides, yield is 98.09%.
Product structure formula is:HOCH2-CH2-S-S-CH2-CH2OH。
Embodiment 2
A kind of preparation method of polythiaether PVC co-stabilizers, comprises the following steps:
In equipped with agitator, thermometer, the four-hole boiling flask of water cooling condensate liquid water knockout drum, 408.4g TGAs are added
Different monooctyl ester, 30% hydrogen peroxide 113.4g, 185g toluene (between above-mentioned isooctyl thioglycolate, 30% hydrogen peroxide, toluene mole
Than for 2:1:2), 4.05g catalyst of triethylamine, stirring reaction 2h at 110 DEG C, then distillation removes organic solvent and obtains
The different monooctyl ester disulfide of 398.4g oxalic acid, yield is 97.6%.
Product structure formula is:(CH3)2CH(CH2)5OCOC-S-S-COCO(CH2)5CH(CH3)2。
Embodiment 3
A kind of preparation method of polythiaether PVC co-stabilizers, comprises the following steps:
In equipped with agitator, thermometer, the four-hole boiling flask of water cooling condensate liquid water knockout drum, 520.88g laurate is added
Mercapto ethyl ester, 30% hydrogen peroxide 113.4g, 212g dimethylbenzene (above-mentioned laurate mercapto ethyl ester, between 30% hydrogen peroxide, dimethylbenzene
Mol ratio be 2:1:2), 5.2g catalyst isobutyramide, stirring reaction 3h at 140 DEG C, then distillation removes organic solvent
508.8g tin dilaurate ethyl ester disulfides are obtained, yield is 98.06%.
Product structure formula is:C11H23COOCHCH-S-S-CHCHOOCC11H23。
Embodiment 4
A kind of preparation method of polythiaether PVC co-stabilizers, comprises the following steps:
In equipped with agitator, thermometer, the four-hole boiling flask of water cooling condensate liquid water knockout drum, 684.24g vegetable oil is added
Sour mercapto ethyl ester, 30% hydrogen peroxide 113.4g, 212g dimethylbenzene (above-mentioned vegetable oil acid mercapto ethyl ester, 30% hydrogen peroxide, dimethylbenzene
Between mol ratio be 2:1:2), 6.85g catalyst isobutyramide, stirring reaction 3h at 140 DEG C, then distillation removing is organic
Solvent obtains the vegetable oil acid ethyl ester disulfides of 669.1g bis-, and yield is 98.07%.
Product structure formula:
CH3(CH2)7CH=CH (CH2)7COOCHCH-S-S-CHCHOOC(CH2)7CH=CH (CH2)7CH3。
Comparative example 1
A kind of preparation method of polythiaether PVC co-stabilizers, product is substantially the same manner as Example 2, and difference is it
Oxidant adopts sulphur, and byproduct of reaction is hydrogen sulfide.
In equipped with agitator, thermometer, the four-hole boiling flask of water cooling condensate liquid water knockout drum, 408.4g TGAs are added
Different monooctyl ester, Cosan 32.06g, 2.45g organic amine catalyst, stirring reaction 2h at 80 DEG C, reaction end gas use NaOH
The aqueous solution absorbs.Jing filter paper is filtrated to get the different monooctyl ester disulfide of 386.2g oxalic acid after most, and yield is 95.03%.
Product structure formula is:(CH3)2CH(CH2)5OCOC-S-S-COCO(CH2)5CH(CH3)2。
Application experiment example 1
Synthesize obtained 5 kinds different polythiaethers with a kind of Commercial epoxy soybean oil and embodiment 1~4, comparative example 1 and help stable
Agent is made into the Methyltin composite heat stabilizer that Theil indices are 16% with commercially available methyl tin heat stabilizer T181 respectively, is designated as respectively
1#、2#、3#、4#、5#、6#.And the Methyltin composite heat stabilizer for obtaining is applied into PVC transparent sheet formulation double roller plasticates examination
In testing, addition is 1.2%, and after polyvinyl chloride resin powder, heat stabilizer and other auxiliary agents are mixed, high temperature carries out twin-roll machine
Plasticate test, at 194 DEG C at interval of sampling in 2 minutes once, until all of sheet material turns yellow.Determine double roller to plasticate the color of sample
Product index b value, so can be with the thermostable effect of effectively control stabilizer.It is more yellow that b values are more just showing as color, more it is negative then
Show as more blue.Its test result is as follows:
Table one:The PVC transparent sheet formulation double roller of Methyltin composite heat stabilizer is plasticated test
Knowable to table one, under the conditions of consumption identical, from terms of thermal stability and the transparency, embodiment of the present invention synthesis
The polythiaether co-stabilizer for the obtaining auxiliary heat stabilizer epoxidized soybean oil maximum better than consumption in industry and existing preparation method
The different monooctyl ester disulfide of oxalic acid for obtaining.
Application experiment example 2
The 5 kinds of different polythiaethers obtained with a kind of commercially available phosphite ester 1500N and embodiment 1~4 and the synthesis of comparative example 1
Co-stabilizer respectively with calcium zinc heat stabilizer compound, addition for compound stabilizer total amount 40%, be designated as respectively 7#, 8#, 9#,
10#、11#、12#.The Ca-Zn composite heat stabilizer for obtaining is applied into the double roller of PVC profile formula to plasticate in test, addition
1.2% is, after the mixing of polyvinyl chloride resin powder, heat stabilizer and other auxiliary agents, high temperature carries out twin-roll machine and plasticates test,
At 194 DEG C at interval of sampling in 3 minutes once, until all of sheet material turns yellow.Determine double roller to plasticate the chromaticity index b value of sample,
So can be with the thermostable effect of effectively control stabilizer.It is more yellow that b values are more just showing as color.Its test result is as follows:
Table two:The PVC profile formula double roller of calcium-zinc composite stabilizing agent is plasticated test
Knowable to table two, from terms of thermal stability, polythiaether co-stabilizer and industry that embodiment of the present invention synthesis is obtained
Conventional anti-" zinc burning " organic auxiliary heat stabilizer phosphite ester 1500N equally has good thermal stability;In consumption phase
With under conditions of, tin dilaurate ethyl ester disulfide and two vegetable oil acid ethyl ester disulfides are than commercially available phosphite ester and existing preparation
The different monooctyl ester disulfide of oxalic acid that method is obtained possesses more preferable long-term thermal stability performance, acts on preferably anti-zinc burning.
Application experiment example 3
With embodiment 1~4 and the different polythiaether co-stabilizers of the synthesis of comparative example 1 obtain 5 kinds respectively with commercially available mercaptan
Antimony heat stabilizer is compounded, and addition is the 2% of compound stabilizer, is designated as 13#, 14#, 15#, 16#, 17# respectively, and with without
The mercaptans type heat stabilizer of polythiaether does reference, is designated as 18#.The mercaptans type composite thermal stabilizer for obtaining is placed in into ultraviolet-visible
In irradiation case, the time of heat stabilizer blackening is observed by the naked eye and recorded, the ultraviolet light stabilized performance of stabilizer is compareed with this.
Experimental result is as follows:
Table three:The ultraviolet light stabilized performance test of mercaptans type compound stabilizer
Knowable to table three, the polythiaether heat stabilizer of embodiment of the present invention synthesis is a kind of fabulous UV light stabilizing agent,
The ultraviolet light stabilized performance and storage performance of raising mercaptans type heat stabilizer that can be by a relatively large margin.In consumption identical condition
Under, the polythiaether heat stabilizer monooctyl ester disulfide more different than the oxalic acid that existing preparation method is obtained of embodiment of the present invention synthesis possesses
More preferable ultraviolet light stability.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope of this specification record is all considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more concrete and detailed, but and
Can not therefore be construed as limiting the scope of the patent.It should be pointed out that for one of ordinary skill in the art comes
Say, without departing from the inventive concept of the premise, some deformations and improvement can also be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be defined by claims.