CN108641019A - A kind of polyvinyl chloride comb-shaped polymer and its preparation method and application that abietyl is Thiolation - Google Patents
A kind of polyvinyl chloride comb-shaped polymer and its preparation method and application that abietyl is Thiolation Download PDFInfo
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- CN108641019A CN108641019A CN201810438934.1A CN201810438934A CN108641019A CN 108641019 A CN108641019 A CN 108641019A CN 201810438934 A CN201810438934 A CN 201810438934A CN 108641019 A CN108641019 A CN 108641019A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
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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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- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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Abstract
A kind of polyvinyl chloride comb-shaped polymer and its preparation method and application that abietyl is Thiolation.The Thiolation polyvinyl chloride comb-shaped polymer of this abietyl reacts, then synthesize to obtain by click-reaction with dithioglycol using the derivative of forestry high-quality resource rosin as raw material with propylene halide.Different amounts of abietyl mercaptan is grafted in alkaline system in PVC strands, obtains the Thiolation polyvinyl chloride comb-shaped polymer of the different abietyl of grafting rate.Rosin group is inserted into PVC molecule interchains, weakens PVC macromolecular chain intermolecular forces so that main chain can preferably flow, and then achieve the purpose that be plasticized PVC.The glass transition temperature of PVC product can be reduced to 34.40 DEG C by this method, elongation at break up to 474.99%, and in distilled water, acid/base solution, vegetable oil esters, mineral oil and organic solvent without the migration of plasticizer.
Description
Technical field
The present invention relates to the chemical modification of macromolecule chemical industry material, the Thiolation polyvinyl chloride comb of specifically a kind of abietyl
Shaped polymer and its preparation method and application.
Background technology
Polyvinyl chloride (PVC) is one of maximum plastics of dosage in the world, is widely used in building materials, Medical treatment device
The fields such as tool, household electrical appliance.Since polyvinyl chloride Interchain interaction power is big, need that a large amount of increasings are added in process
Agent is moulded to reduce macromolecular interchain interaction, achievees the purpose that improve processing performance, softening product.Phthalate is
The most plasticizer of industrial dosage.Since phthalate molecular weight is low, volatility resistance, solvent resistant extractable compare
Difference is easy to be absorbed and be accumulated in human body, and teratogenesis is carcinogenic.Therefore, people there is an urgent need to develop go out it is a kind of it is novel it is safe and non-toxic,
The plasticizer of environmentally friendly and resistance to migration.
China's rosin is resourceful, and rosin volume of trade accounts for about the 60% of world's total amount, and wherein ROSIN INDUSTRY is even more China woods
One of four big pillar industry of industry, is known as " rising industry ".Rosin is acid (about 90%) and neutral (about 10%) compound
Mixture.Acidic components are commonly known as rosin (or resin) acid, and mainly containing colophony type sour (40-60%) and Korean pine acid type
(9-27%) acid.The agent structure of rosin acid is the stiffening ring being similar in molecule containing there are two the luxuriant and rich with fragrance structure of the tricyclic two of double bond
Shape aliphatic series or aromatic compounds, and connect a carboxyl.Therefore, it by the reaction of carboxylic acid group and carbon-to-carbon double bond, can obtain
Rosin derivative.The Rosinyl plasticizer synthesized using rosin and its derivative is good, degradable with plasticizing capacity, pollution is small,
The features such as nontoxic is Environment-friendlyplasticizer plasticizer.
Plasticizer and its physical blending are used mostly to the processing and forming of PVC at present, but this is that a thermodynamics is incompatible
System, the active force only relied between the two are insufficient to allow stable system to exist.Therefore plasticiser can be continuous in use
It is oozed out from PVC, declines to PVC product functions and even lose, the plasticizer of some exudations also pollutes the environment, and harmful to human is strong
Health.Therefore solve the problems, such as that plasticizer property easy to migrate develops the hot spot with application as plasticizer.It will be plasticized by chemical method
Agent is grafted on PVC macromolecular chains i.e. to its internal plasticization, fundamentally solves the disadvantage of plasticizer resistance to migration difference, is a kind of
Feasible and effective means.
Invention content
The technical issues of solution：The present invention provides a kind of polyvinyl chloride comb-shaped polymer that abietyl is Thiolation and its preparation
Methods and applications.
Technical solution：A kind of polyvinyl chloride comb-shaped polymer that abietyl is Thiolation, general structure are：
R isN=320~960,
M=27~482.
The preparation method of the Thiolation polyvinyl chloride comb-shaped polymer of abietyl, it is and halogenated using rosin derivative as raw material
Propylene reaction is made abietyl acrylic ester, then synthesizes by click-reaction with dithioglycol to obtain abietyl mercaptan；Abietyl sulphur
Alcohol obtains abietyl mercaptides in alkaline system, in being grafted to PVC strands, obtains the Thiolation polychlorostyrene of abietyl
Ethylene comb-shaped polymer.
Preferably, the rosin derivative is dehydroabietic acid or hydrogenated rosin.
Preferably, the propylene halide is chloropropene or bromopropene.
Preferably, the rosin derivative and propylene halide molar ratio are 1:(1~5)；The abietyl acrylic ester and second
The molar ratio of two mercaptan is 1:(1~3).
Preferably, the alkaline system is sodium methoxide-methanol, sodium ethoxide-ethyl alcohol, sodium propoxide-propyl alcohol, sodium carbonate/carbonic acid
Any one in hydrogen sodium-cyclohexanone/N,N-dimethylformamide.
Preferably, the molar ratio of the abietyl mercaptan and alkali is 1:1.
Preferably, the molar ratio of the abietyl mercaptides and PVC are respectively 0.2:1(PVCR-1)、0.5:1(PVCR-
2)、 0.7:1(PVCR-3)、1:1(PVCR-4)。
Preferably, the abietyl mercaptides graft reaction temperature is 50~100 DEG C, and the time of the graft reaction is 4
~10h.
Application of the Thiolation polyvinyl chloride comb-shaped polymer of above-mentioned abietyl in preparing PVC blends.
Chemical reaction mechanism：Its reaction mechanism can be indicated by following synthesis paths：
The first step：The synthesis of abietyl mercaptan
Second step：The synthesis of the Thiolation polyvinyl chloride comb-shaped polymer of abietyl
Advantageous effect：Compared with prior art, the polyvinyl chloride comb-shaped polymer that the current country there is no abietyl Thiolation
Synthetic method report, the present invention is pioneering.The present invention is using the derivative of natural reproducible rosin as raw material, and raw material sources are rich
Richness, synthesis technology is simple, and production cost is low, superior product quality.Products obtained therefrom toxic side effect of the present invention is small, abietyl mercaptan pair
PVC plays a kind of internal plasticization, and solvent-free extraction, stability is strong, and heat resistance is preferable.This method can be by PVC product
Glass transition temperature is reduced to 34.40 DEG C, elongation at break up to 474.99%, and distilled water, acid/base solution, plant
In object grease, mineral oil and organic solvent without the migration of plasticizer.
Description of the drawings
The DSC curve of Fig. 1 PVC；
The DSC curve of internal plasticization PVC material prepared by Fig. 2 embodiments 2.
Specific implementation mode
Below in conjunction with the embodiment of the present invention, clear, complete description that technical solution in the embodiment of the present invention carries out,
Obviously, the embodiment described is only merely the section Example of the present invention, instead of all the embodiments.
The synthesis of dehydrogenation rosin-base mercaptan
In the embodiment of the present invention, the synthetic method of dehydrogenation rosin-base mercaptan is needed by following below scheme：To equipped with reflux
60g dehydroabietic acids (0.2mol), 27.6g K are added in the 500mL three neck round bottom of condenser2CO3With 50mL acetone.Then
The solution for the 48.4g bromopropenes (0.4mol) being dissolved in 20mL acetone is added dropwise at 50 DEG C.Mixture flows back 12 at 70 DEG C
After hour, stops reacting and being cooled to room temperature, then use dichloromethane (CH2Cl2) washing.Organic phase is collected by extraction to be used in combination
It distills water washing three times, then removes solvent, the dehydrogenated rosin acrylic ester of yellow in a rotary evaporator at 80 DEG C.Finally,
It is dried into 6h in 80 DEG C of vacuum drying oven, obtains the final product (yield that weight is 63.1g：92%).In 150mL grounds
51.4g dehydrogenated rosins acrylic ester (0.15mol), 28.3g dithioglycols (0.3mol), 0.5g photoinitiators-are added in conical flask
6512, BDK (1wt%) and 50mL tetrahydrofurans (THF), then room temperature magnetic agitation is reacted for 24 hours under ultraviolet light.Pass through
Vacuum distillation removes solvent and unreacted dithioglycol, and the dehydrogenation rosin-base mercaptan of yellow is made.
The synthesis of hydrogenated rosin base mercaptan
In the embodiment of the present invention, the synthetic method of hydrogenated rosin base mercaptan is needed by following below scheme：To equipped with reflux
The refined hydrogenation abietic acids (0.2mol) of 61.4g, 27.6g K are added in the 500mL three neck round bottom of condenser2CO3With 50mL third
Ketone.Then the solution for the 48.4g bromopropenes (0.4mol) being dissolved in 20mL acetone is added dropwise at 50 DEG C.Mixture is at 70 DEG C
After reflux 12 hours, stops reacting and being cooled to room temperature, then use dichloromethane (CH2Cl2) washing.It is organic by extracting collection
It mutually and is washed with distilled water three times, then removes solvent, white hydrogenated rosin acrylic ester in a rotary evaporator at 80 DEG C.
Finally, it is dried to 6h in 80 DEG C of vacuum drying oven, obtains the final product (yield that weight is 63.1g：92%).
51.4g hydrogenated rosins acrylic ester (0.15mol), 28.3g dithioglycols (0.3mol), 0.5g are added in 150mL ground conical flasks
Photoinitiator -6512, BDK (1wt%) and 50mL tetrahydrofurans (THF), then room temperature magnetic agitation is anti-under ultraviolet light
It should for 24 hours.Solvent and unreacted dithioglycol are removed by vacuum distillation, the hydrogenated rosin base mercaptan of white is made.
Embodiment 1
In the embodiment of the present invention, the synthetic method of the Thiolation polyvinyl chloride comb-shaped polymer of dehydrogenation rosin-base need by
Following below scheme：In N2Under protection, 30g dehydrogenation rosin-base mercaptan is pressed and sodium methoxide molar ratio 1:1 is added sodium methoxide-methanol system
In (methanol 100mL), after 70 DEG C of return stirring 10h, solvent methanol is removed with vacuum distillation after reaction, obtains dehydrogenated rosin
Base sodium mercaptides crude product.It uses petroleum ether crude product multiple repeatedly, removes unreacted mercaptan, filter, vacuum is dry at 60 DEG C
Dry 4h obtains yellowish dehydrogenation rosin-base sodium mercaptides solid.In N2Under protection, PVC is dissolved in THF, is added and chlorine atom mole
Than the dehydrogenation rosin-base sodium mercaptides for 0.2, after 50 DEG C are reacted 4h, reaction terminates, and pours the mixture into methanol and is precipitated and washs,
It filters, drying for 24 hours, obtains the Thiolation polyvinyl chloride comb-shaped polymer of the dehydrogenation rosin-base of white solid at 60 DEG C.Take 3g
Comb-shaped polymer is dissolved to limpid with 40mL THF, then pours into solution in culture dish (d=19cm), at room temperature volatilization from
It is put into after assembling film forming and continues the dry THF for removing trace for 24 hours in 50 DEG C of air dry oven.
Resistance to volatilization test (according to ISO176-2005 standards) carried out to prepared PVC film and resistance to migration test (according to
ASTM D1239-98 standards) display, migration of plasticizer is effectively suppressed in sample, and quality is also almost in volatility test
There is not loss.Its glass transformation temperature is reduced to 52.9 DEG C from 87 DEG C.By Erichsen test (according to GB/T 1040.1-
2006) it measures it and is broken elongation at break 394.05%, elasticity modulus 0.58MPa.
Embodiment 2
In the embodiment of the present invention, the synthetic method of the Thiolation polyvinyl chloride comb-shaped polymer of dehydrogenation rosin-base need by
Following below scheme：In N2Under protection, 30g dehydrogenation rosin-base mercaptan is pressed and sodium ethoxide molar ratio 1:1 is added sodium ethoxide-ethyl alcohol (second
100 mL of alcohol) in system, after 70 DEG C of return stirring 10h, etoh solvent is removed with vacuum distillation after reaction, obtain dehydrogenation pine
Perfume base sodium mercaptides crude product.It uses petroleum ether crude product multiple repeatedly, removes unreacted mercaptan, filter, vacuum at 60 DEG C
Dry 4h obtains yellowish dehydrogenation rosin-base sodium mercaptides solid.In N2Under protection, PVC is dissolved in THF, addition rubs with chlorine atom
That is than being 0.5 dehydrogenation rosin-base sodium mercaptides, and after 50 DEG C are reacted 6h, reaction end, which is poured the mixture into methanol, to be precipitated and wash,
It filters, drying for 24 hours, obtains the Thiolation polyvinyl chloride comb-shaped polymer of the dehydrogenation rosin-base of white solid at 60 DEG C.Take 3g
Comb-shaped polymer is dissolved to limpid with 40mL THF, then pours into solution in culture dish (d=19cm), at room temperature volatilization from
It is put into after assembling film forming and continues the dry THF for removing trace for 24 hours in 50 DEG C of air dry oven.
Resistance to volatilization test (according to ISO176-2005 standards) carried out to prepared PVC film and resistance to migration test (according to
ASTM D1239-98 standards) display, migration of plasticizer is effectively suppressed in sample, and quality is also almost in volatility test
There is not loss.Its glass transformation temperature is reduced to 34.40 DEG C from 87 DEG C.By Erichsen test (according to GB/T 1040.1-
2006) it measures it and is broken elongation at break 474.99%, elasticity modulus 0.89MPa.
Embodiment 3
In the embodiment of the present invention, the synthetic method of the Thiolation polyvinyl chloride comb-shaped polymer of hydrogenated rosin base need by
Following below scheme：In N2Under protection, 30g hydrogenated rosin base mercaptan is pressed and sodium carbonate molar ratio 1:1 is added sodium carbonate-cyclohexanone
In (cyclohexanone 100mL) system, after stirring 10h at 100 DEG C, solvent cyclohexanone is removed with vacuum distillation after reaction, is obtained
Hydrogenated rosin base sodium mercaptides crude product.It uses petroleum ether crude product multiple repeatedly, removes unreacted mercaptan, filter, 60 DEG C
Lower vacuum drying 4h obtains white yellow hydrogenated rosin base sodium mercaptides solid.In N2Under protection, PVC is dissolved in THF, addition and chlorine
Atomic molar ratio is 1 hydrogenated rosin base sodium mercaptides, and after 50 DEG C are reacted 6h, reaction end, which is poured the mixture into methanol, to be precipitated simultaneously
Washing filters, drying for 24 hours, obtains the Thiolation polyvinyl chloride comb-shaped polymer of the hydrogenated rosin base of white solid at 60 DEG C.
It takes 3g comb-shaped polymers to be dissolved to 40mL THF limpid, then solution is poured into culture dish (d=19 cm), is waved at room temperature
It is put into after assembling film forming and continues the dry THF for removing trace for 24 hours in 50 DEG C of air dry oven.
Resistance to volatilization test (according to ISO176-2005 standards) carried out to prepared PVC film and resistance to migration test (according to
ASTM D1239-98 standards) display, migration of plasticizer is effectively suppressed in sample, and quality is also almost in volatility test
There is not loss.Its glass transformation temperature is reduced to 40.1 DEG C from 87 DEG C.By Erichsen test (according to GB/T 1040.1-
2006) it measures it and is broken elongation at break 468.81%, elasticity modulus 0.54MPa.
Claims (10)
1. a kind of polyvinyl chloride comb-shaped polymer that abietyl is Thiolation, it is characterised in that general structure is：
R isN=320~960, m=
27~482.
2. the preparation method of the Thiolation polyvinyl chloride comb-shaped polymer of abietyl according to claim 1, it is characterised in that
Using rosin derivative as raw material, is reacted with propylene halide and abietyl acrylic ester is made, then closed by click-reaction with dithioglycol
At obtaining abietyl mercaptan；Abietyl mercaptan obtains abietyl mercaptides in alkaline system, is being grafted to PVC strands
In, obtain the Thiolation polyvinyl chloride comb-shaped polymer of abietyl.
3. the preparation method of the Thiolation polyvinyl chloride comb-shaped polymer of abietyl according to claim 2, it is characterised in that
The rosin derivative is dehydroabietic acid or hydrogenated rosin.
4. the preparation method of the Thiolation polyvinyl chloride comb-shaped polymer of abietyl according to claim 2, it is characterised in that
The propylene halide is chloropropene or bromopropene.
5. the preparation method of the Thiolation polyvinyl chloride comb-shaped polymer of abietyl according to claim 2, it is characterised in that
The rosin derivative is 1 with propylene halide molar ratio:(1~5)；The molar ratio of the abietyl acrylic ester and dithioglycol is
1:(1~3).
6. the preparation method of the Thiolation polyvinyl chloride comb-shaped polymer of abietyl according to claim 2, it is characterised in that
The alkaline system is sodium methoxide-methanol, sodium ethoxide-ethyl alcohol, sodium propoxide-propyl alcohol, sodium carbonate/bicarbonate-cyclohexanone/N, N-
Any one in dimethylformamide.
7. the preparation method of the Thiolation polyvinyl chloride comb-shaped polymer of abietyl according to claim 2, it is characterised in that
The molar ratio of the abietyl mercaptan and alkali is 1:1.
8. the preparation method of the Thiolation polyvinyl chloride comb-shaped polymer of abietyl according to claim 2, it is characterised in that
The molar ratio of the abietyl mercaptides and PVC are respectively 0.2:1(PVCR-1)、0.5:1(PVCR-2)、0.7:1(PVCR-3)、
1:1(PVCR-4)。
9. the preparation method of the Thiolation polyvinyl chloride comb-shaped polymer of abietyl according to claim 2, it is characterised in that
The abietyl mercaptides graft reaction temperature is 50~100 DEG C, and the time of the graft reaction is 4~10h.
10. Thiolation polyvinyl chloride comb-shaped polymer the answering in preparing PVC blends of abietyl described in claim 1
With.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115322461A (en) * | 2022-07-21 | 2022-11-11 | 青岛橡六胶管有限公司 | Rubber tube suitable for hydraulic transmission under mine and preparation method thereof |
| CN115677547A (en) * | 2022-10-27 | 2023-02-03 | 中国林业科学研究院林产化学工业研究所 | Tung oil-based plasticizer and preparation method thereof |
| CN118388902A (en) * | 2024-06-26 | 2024-07-26 | 浙江正泰建筑电器有限公司 | High-flame-retardance heat-stability modified polyvinyl chloride material and preparation method thereof |
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Cited By (5)
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| CN115677547A (en) * | 2022-10-27 | 2023-02-03 | 中国林业科学研究院林产化学工业研究所 | Tung oil-based plasticizer and preparation method thereof |
| CN115677547B (en) * | 2022-10-27 | 2024-05-28 | 中国林业科学研究院林产化学工业研究所 | Tung oil-based plasticizer and preparation method thereof |
| CN118388902A (en) * | 2024-06-26 | 2024-07-26 | 浙江正泰建筑电器有限公司 | High-flame-retardance heat-stability modified polyvinyl chloride material and preparation method thereof |
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