CN107383276A - A kind of thiocarbamide analog copolymer heat stabilizer and preparation method thereof - Google Patents
A kind of thiocarbamide analog copolymer heat stabilizer and preparation method thereof Download PDFInfo
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- CN107383276A CN107383276A CN201710533125.4A CN201710533125A CN107383276A CN 107383276 A CN107383276 A CN 107383276A CN 201710533125 A CN201710533125 A CN 201710533125A CN 107383276 A CN107383276 A CN 107383276A
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
- C08F220/603—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen and containing oxygen in addition to the carbonamido oxygen and nitrogen
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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
Abstract
The present invention relates to a kind of thiocarbamide analog copolymer heat stabilizer and preparation method thereof; the heat stabilizer is to be made by 4 (3 benzoylthioureas base) phenylacrylic acid ester monomers and acrylamide N Hete rocyclic derivatives monomers by free radicals copolymerization reaction, and its general structure is：Wherein, R is
Description
Technical field
The present invention relates to polyvinyl chloride processing additives heat stabilizer field, and in particular to a kind of thiocarbamide analog copolymer heat is steady
Determine agent and preparation method thereof.
Background technology
Polyvinyl chloride has the advantages that intensity is high and can be plasticized, be corrosion-resistant, be fire retardant, good insulating, the transparency are high, is building
It is material, industrial product, commodity, flooring laminate, floor tile, artificial leather, tubing, electric wire, packaging film, bottle, expanded material, close
Closure material, fiber etc. are widely used.But in polyvinyl chloride actual polymerisation process, it may occur that many side reactions, make
More defect sturcture in the molecular structure of polyvinyl chloride be present, therefore polyvinyl chloride is made by temperature, pressure in process
Occur to remove hcl reaction with easy, polyvinyl chloride degradation property is greatly affected, and influences processing and practical application.
Heat stabilizer is added when polyvinyl chloride is processed effectively can suppress or slow down the degraded dechlorination of polyvinyl chloride
Change hydrogen.Such as lead salt heat stabilizer, thermal stability is excellent, but it is unfriendly to environment and progressively exit heat stabilizer industry,
Current environment-protecting and non-poisonous heat stabilizer enjoys favor, and calcium/zinc heat stabilizer of such as generally acknowledged asepsis environment-protecting is widely used.
In recent years, heat stabilizer research field is concentrated mainly on nontoxic, field of Environment Protection, environment-protecting and non-poisonous organic thermostabilization
Agent progresses into the visual field of heat stabilizer researcher.Chinese patent CN105949667A disclose a kind of organic barium of beta-diketon class/
Zinc polychloroethylene heat stabilizer and preparation method thereof, although the organic barium of beta-diketon class/zinc polyvinyl chloride heat prepared by this method is steady
Determine the advantage that agent combines barium/zinc stabilizer and beta-diketone compounds auxiliary heat stabilizer, but the heat stabilizer used
" zinc burning " phenomenon in journey be present, influence the thermal stability of the heat stabilizer.Chinese patent CN105936679A discloses one kind
Maleic acid list polyvinyl alcohol ester barium salt heat stabilizer and preparation method thereof, heat stabilizer prepared by this method act solely on polychlorostyrene
Thermal stability is poor during ethene, it is impossible to is used alone, it is necessary to can just show certain thermostabilization with being applied in combination with zinc soap
Performance.Chinese patent CN105885087A discloses a kind of new polychloroethylene heat stabilizer two (pyridin-4-yl methyl) sulfane
Adipic acid zinc, although the heat stabilizer can adsorb free hydrogen chloride, can also there is " zinc burning " phenomenon, it is steady to influence the heat
Determine the thermostable effect of agent.
Organic type thermal stabilizing agent is environmentally friendly, belongs to environment-protecting and non-poisonous heat stabilizer, research it is more be all
Organic molecule, but its cannot function as main heat stabilizer be used alone improve the heat endurance of polyvinyl chloride, it is necessary to main heat
Compound stabilizer is using can just show excellent thermal stability.The present invention is with 4- (3- benzoylthioureas base) phenylpropen
Acid ester monomer is copolymerized with acrylamide N Hete rocyclic derivatives monomer radical, is prepared for side chain and is contained disubstituted thiourea and N heterocycle knots
The thiocarbamide analog copolymer heat stabilizer of structure, disubstituted thiourea structure can substitute the unstable chlorine atom in polyvinyl chloride chain, and
Imido grpup and alkaline N heterocyclic groups in molecular side chain can quick absorbing hydrogen chloride, polymer thermostable prepared by the present invention
Agent can improve the heat endurance of polyvinyl chloride by substituting unstable chlorine atom and absorbing hydrogen chloride two ways, in structure
Ester group increase and the compatibility of polyvinyl chloride.
The content of the invention
Technical problem：It is an object of the invention to provide a kind of thiocarbamide analog copolymer heat stabilizer and preparation method thereof, the party
Thiocarbamide analog copolymer heat stabilizer prepared by method has preferable compatibility with polyvinyl chloride, can suppress the self-catalysis of hydrogen chloride, carry
The heat endurance of high polyvinyl chloride, and the heat stabilizer is environmentally friendly nontoxic.In addition, the heat stabilizer can also and other
Heat stabilizer such as hydrotalcite heat stabilizer compounding use, has cooperative effect, and the heat that can be improved after heat stabilizer compounding is steady
Qualitative energy.
Technical scheme：A kind of thiocarbamide analog copolymer heat stabilizer of the present invention is by 4- (3- benzoylthioureas base) phenyl
Acrylate monomer and acrylamide N Hete rocyclic derivatives monomers are made by free radicals copolymerization reaction, and its general structure is：
Wherein, R isIn one kind, degree of polymerization X be 300~500, polymerization
It is 600~1000 to spend Y.
The preparation method of thiocarbamide analog copolymer heat stabilizer of the present invention is：
A, at room temperature, the ammonium thiocyanate acetone soln that concentration is 100~150g/L is added in reactor, by benzoyl
Chlorine is with ammonium thiocyanate mass ratio：0.5：1~1:1, chlorobenzoyl chloride is added in reactor, after room temperature reaction, centrifuged,
Benzoyl isothiocyanate acetone mixture is obtained, is 0.7 by para-aminophenol and chlorobenzoyl chloride mass ratio：1~0.9:1, will
Para-aminophenol is added in above-mentioned benzoyl isothiocyanate acetone mixture, heating, reaction, by acryloyl chloride and benzoyl
Chlorine mass ratio is 0.5：1~0.9:1, acryloyl chloride is added in above-mentioned reaction solution, after heating, reaction, room temperature is down to, centrifuges
Separation, is obtained 4- (3- benzoylthioureas base) phenyl acrylate, is washed with the absolute ethyl alcohol of 4~6 times of chlorobenzoyl chloride quality
Wash, be dried in vacuo, obtain 4- (3- benzoylthioureas base) phenylacrylic acid ester monomer；
B, at room temperature, the acrylamide acetone soln that concentration is 150~200g/L is added in reactor, by N heterocycles
Formic acid is 1 with acrylamide mol ratio:1~2:1, N heterocyclic formics are added in reactor, after heating, reaction, are down to room temperature,
Centrifuge, obtain acrylamide N Hete rocyclic derivatives, washed with the absolute ethyl alcohol of 2~4 times of acrylamide quality, vacuum is done
It is dry, obtain acrylamide N Hete rocyclic derivatives monomers；
C, at room temperature, it is obtained 4- (3- benzoylthioureas base) phenyl third in 150~260g/L step a by concentration
The DMF solution of olefin(e) acid ester monomer adds reactor, by acrylamide N Hete rocyclic derivatives monomer and 4- (3- benzene
Formoxyl ghiourea group) phenyl acrylate monomer mole ratio be 1：1~3:1, add in the step b that concentration is 150~300g/L
The DMF solution of obtained acrylamide N Hete rocyclic derivatives monomers, after mixing, by azo-initiator and 4-
(3- benzoylthioureas base) phenyl acrylate monomer weight ratio is 0.005:1~0.2:1, azo-initiator is added anti-
Kettle is answered, microwave radiation technology reaction, room temperature is cooled to after reaction, by anhydrous alcohols solvent and 4- (3- benzoylthioureas base) phenyl third
The mass ratio of olefin(e) acid ester monomer is 2:1~5:1, anhydrous alcohols solvent is added, after stirring 30~50min, centrifuges, is gathered
Compound heat stabilizer, with the anhydrous alcohols solvent of 2~3 times of 4- (3- benzoylthioureas base) phenyl acrylate monomer mass
Washing, vacuum drying, obtains thiocarbamide analog copolymer heat stabilizer.
Wherein：
Being added to para-aminophenol in above-mentioned benzoyl isothiocyanate acetone mixture described in step a, heating
Reaction, its temperature are 40~60 DEG C, and the reaction time is 3~6h.
Adding acryloyl chloride in above-mentioned reaction solution described in step a, temperature reaction, its temperature are 70~85 DEG C,
Reaction time is 6~8h.
Vacuum drying described in step a, its temperature are 50~60 DEG C, and the time is 8~10h.
N heterocyclic formics described in step b are N- piperazinecarboxylic acids, one kind in 3- pyrrolidinecarboxylic acids, 4- piperidinecarboxylic acids.
N heterocyclic formics are added in reactor in step b, temperature reaction, its temperature is 60~80 DEG C, and the time is 7~9h.
Vacuum drying described in step b, its temperature are 40~50 DEG C, and the time is 8~10h.
Azo-initiator described in step c is ABVN or azo-bis-iso-dimethyl.
Anhydrous alcohols solvent described in step c is absolute methanol or absolute ethyl alcohol.
Azo-initiator is added to reactor described in step c, microwave radiation technology reaction, its reaction temperature is 55~80
DEG C, the reaction time is 15~30min.
Vacuum drying temperature described in step c is 60~80 DEG C, and the time is 8~10h.
The performance test methods of above-mentioned thiocarbamide analog copolymer heat stabilizer are：
Using national standard GB2917.1-2002 Congo Red tests method test polyvinyl-chloride use thiocarbamide analog copolymer heat stabilizer
Thermal stability, Congo red test is carried out using SG-5 types polyvinyl chloride, with thiocarbamide analog copolymer heat stabilizer and polyvinyl chloride
Mass ratio is 10：100, thiocarbamide analog copolymer heat stabilizer is uniformly tested with polyvinyl chloride in ground and mixed in mortar.
Record Congored test paper begins to change into the time of blueness, and as heat-stable time Ts, heat-stable time Ts is longer, heat stabilizer
Thermal stability is better.
Beneficial effect：A kind of thiocarbamide analog copolymer heat stabilizer of the present invention has the advantages that：
1st, the thiocarbamide analog copolymer heat stabilizer for preparing of the present invention, can in polyvinyl chloride process with its distinctive two
Unstable chlorine atom in substituting thioureido structure substitution polyvinyl chloride chain, forms stable structure, reduces the formation of conjugated system,
Improve the heat endurance of polyvinyl chloride.
2nd, it is miscellaneous containing alkaline imido grpup and alkaline N in the molecular side chain of thiocarbamide analog copolymer heat stabilizer prepared by the present invention
Cyclic group structure, caused hydrogen chloride in polyvinyl chloride process can be quickly absorbed, suppress the autocatalysis of hydrogen chloride,
Improve the thermal stability of polyvinyl chloride.
3rd, the ester group in the thiocarbamide analog copolymer heat stabilizer for preparing of the present invention has a lubrication, can be with process
Improve the greasy property of polyvinyl chloride.
4th, the heat stabilizer can also have collaboration effect with other heat stabilizers such as hydrotalcite heat stabilizer compounding use
Should, the thermal stability after heat stabilizer compounding can be improved.
5th, it is of the invention by the disubstituted thiourea functional structure with heat stabilization, basic group imido grpup, alkaline N heterocycles
Group and lubricating moiety ester group etc., which combine, carries out Molecular Design, and the thiocarbamide analog copolymer heat stabilizer of preparation is same
When have the function that to substitute polyvinyl chloride unstable chlorine atom and absorbing hydrogen chloride, thermal stability to significantly improve, improve simultaneously
The compatibility of polymer and polyvinyl chloride, makes heat stabilizer fully be contacted with polyvinyl chloride compatible, make it possess heat stabilizer,
The function such as antioxidant and lubricant, it is a kind of novel and multifunctional thiocarbamide analog copolymer heat stabilizer..
Embodiment
A kind of thiocarbamide analog copolymer heat stabilizer provided by the invention is by 4- (3- benzoylthioureas base) phenylpropen
Acid ester monomer and acrylamide N Hete rocyclic derivatives monomers are made by free radicals copolymerization reaction, and its general structure is：
Wherein, R isIn one kind, degree of polymerization X be 300~500, polymerization
It is 600~1000 to spend Y.
The preparation method of above-mentioned this thiocarbamide analog copolymer heat stabilizer is：
A, at room temperature, the ammonium thiocyanate acetone soln that concentration is 100~150g/L is added in reactor, by benzoyl
Chlorine is with ammonium thiocyanate mass ratio：0.5：1~1:1, chlorobenzoyl chloride is added in reactor, after room temperature reaction, centrifuged,
Benzoyl isothiocyanate acetone mixture is obtained, is 0.7 by para-aminophenol and chlorobenzoyl chloride mass ratio：1~0.9:1, will
Para-aminophenol is added in above-mentioned benzoyl isothiocyanate acetone mixture, heating, reaction, by acryloyl chloride and benzoyl
Chlorine mass ratio is 0.5：1~0.9:1, acryloyl chloride is added in above-mentioned reaction solution, after heating, reaction, room temperature is down to, centrifuges
Separation, is obtained 4- (3- benzoylthioureas base) phenyl acrylate, is washed with the absolute ethyl alcohol of 4~6 times of chlorobenzoyl chloride quality
Wash, be dried in vacuo, obtain 4- (3- benzoylthioureas base) phenylacrylic acid ester monomer；
B, at room temperature, the acrylamide acetone soln that concentration is 150~200g/L is added in reactor, by N heterocycles
Formic acid is 1 with acrylamide mol ratio:1~2:1, N heterocyclic formics are added in reactor, after heating, reaction, are down to room temperature,
Centrifuge, obtain acrylamide N Hete rocyclic derivatives, washed with the absolute ethyl alcohol of 2~4 times of acrylamide quality, vacuum is done
It is dry, obtain acrylamide N Hete rocyclic derivatives monomers；
C, at room temperature, it is obtained 4- (3- benzoylthioureas base) phenyl third in 150~260g/L step a by concentration
The DMF solution of olefin(e) acid ester monomer adds reactor, by acrylamide N Hete rocyclic derivatives monomer and 4- (3- benzene
Formoxyl ghiourea group) phenyl acrylate monomer mole ratio be 1：1~3:1, add in the step b that concentration is 150~300g/L
The DMF solution of obtained acrylamide N Hete rocyclic derivatives monomers, after mixing, by azo-initiator and 4-
(3- benzoylthioureas base) phenyl acrylate monomer weight ratio is 0.005:1~0.2:1, azo-initiator is added anti-
Kettle is answered, microwave radiation technology reaction, room temperature is cooled to after reaction, by anhydrous alcohols solvent and 4- (3- benzoylthioureas base) phenyl third
The mass ratio of olefin(e) acid ester monomer is 2:1~5:1, anhydrous alcohols solvent is added, after stirring 30~50min, centrifuges, is gathered
Compound heat stabilizer, with the anhydrous alcohols solvent of 2~3 times of 4- (3- benzoylthioureas base) phenyl acrylate monomer mass
Washing, vacuum drying, obtains thiocarbamide analog copolymer heat stabilizer.
N heterocyclic formics described in the preparation method of above-mentioned this thiocarbamide analog copolymer heat stabilizer are N- piperazine first
One kind in acid, 3- pyrrolidinecarboxylic acids, 4- piperidinecarboxylic acids；Described azo-initiator is that ABVN or azo two are different
Butyric acid dimethyl ester；Described anhydrous alcohols solvent is absolute methanol or absolute ethyl alcohol.
Embodiment 1：
A, 25 DEG C, 1.2L 100g/L ammonium thiocyanate acetone soln is added in reactor, by 120g benzene first in 0.5h
Acyl chlorides is added in reactor, after 25 DEG C of reaction 1h, is centrifuged, benzoyl isothiocyanate acetone mixture is obtained, by 96g
Para-aminophenol is added in above-mentioned benzoyl isothiocyanate acetone mixture, is warming up to 40 DEG C, 3h is reacted, by 78g propylene
Acyl chlorides is added in above-mentioned reaction solution, is warming up to 70 DEG C, after reacting 6h, is down to room temperature, is centrifuged, is obtained 4- (3- benzoyls
Base ghiourea group) phenyl acrylate, is washed 3 times with 400g absolute ethyl alcohols, 60 DEG C of vacuum drying 10h, obtains 4- (3- benzoyls
Ghiourea group) phenylacrylic acid ester monomer；
B, 25 DEG C, 1.2L 150g/L acrylamide acetone soln is added in reactor, by 330g N- piperazine first
Acid is added in reactor, is warming up to 60 DEG C, after reacting 7h, is down to room temperature, is centrifuged, is obtained N- acryloylpiperazines formyls
Amine, washed with 360g absolute ethyl alcohols, 40 DEG C of vacuum drying 10h, obtain N- acryloylpiperazines formyl amine monomers；
C, 25 DEG C, by obtained 4- in 0.6L 150g/L step a (3- benzoylthioureas base) phenyl acrylate list
The DMF solution of body adds reactor, adds obtained N- acryloyl groups piperazine in 0.6L 200g/L step b
The DMF solution of piperazine formyl amine monomers, after mixing, 10g ABVNs are added into reactor, 55 DEG C micro-
Ripple assisted reaction 15min, microwave power 100W, room temperature is cooled to after reaction, adds 300g absolute ethyl alcohols, after stirring 30min,
Centrifuge, obtain thiocarbamide analog copolymer heat stabilizer, washed 3 times, 80 DEG C of vacuum drying 10h, obtained with 200g absolute ethyl alcohols
Thiocarbamide analog copolymer heat stabilizer.
The Congo red heat-stable time Ts of the thiocarbamide analog copolymer heat stabilizer is 30min.
Embodiment 2：
A, 25 DEG C, 1.2L 100g/L ammonium thiocyanate acetone soln is added in reactor, by 60g benzoyls in 1h
Chlorine is added in reactor, after 25 DEG C of reaction 2h, is centrifuged, benzoyl isothiocyanate acetone mixture is obtained, by 51g pairs
Amino-phenol is added in above-mentioned benzoyl isothiocyanate acetone mixture, is warming up to 60 DEG C, 6h is reacted, by 45g acryloyls
Chlorine is added in above-mentioned reaction solution, is warming up to 85 DEG C, after reacting 8h, is down to room temperature, is centrifuged, is obtained 4- (3- benzoyls
Ghiourea group) phenyl acrylate, is washed 3 times with 200g absolute ethyl alcohols, 60 DEG C of vacuum drying 10h, obtains 4- (3- benzoyl sulphur
Urea groups) phenylacrylic acid ester monomer；
B, 25 DEG C, 1.2L 200g/L acrylamide acetone soln is added in reactor, by 440g N- piperazine first
Acid is added in reactor, is warming up to 80 DEG C, after reacting 9h, is down to room temperature, is centrifuged, is obtained N- acryloylpiperazines formyls
Amine, washed with 480g absolute ethyl alcohols, 40 DEG C of vacuum drying 10h, obtain N- acryloylpiperazines formyl amine monomers；
C, 25 DEG C, by obtained 4- in 0.6L 260g/L step a (3- benzoylthioureas base) phenyl acrylate list
The DMF solution of body adds reactor, adds obtained N- acryloyl groups piperazine in 0.6L 280g/L step b
The DMF solution of piperazine formyl amine monomers, after mixing, 15g azo-bis-iso-dimethyls are added into reactor,
70 DEG C of microwave radiation technologies react 30min, microwave power 200W, and room temperature is cooled to after reaction, add 450g absolute methanols, stirring
After 50min, centrifuge, obtain thiocarbamide analog copolymer heat stabilizer, washed 3 times with 350g absolute methanols, 80 DEG C of vacuum drying
10h, obtain thiocarbamide analog copolymer heat stabilizer.
The Congo red heat-stable time Ts of the thiocarbamide analog copolymer heat stabilizer is 34min.
Embodiment 3：
A, 25 DEG C, 1.2L 120g/L ammonium thiocyanate acetone soln is added in reactor, by 86g benzene first in 0.5h
Acyl chlorides is added in reactor, after 25 DEG C of reaction 1.5h, is centrifuged, is obtained benzoyl isothiocyanate acetone mixture, will
73g para-aminophenol is added in above-mentioned benzoyl isothiocyanate acetone mixture, is warming up to 40 DEG C, 6h is reacted, by 65g third
Alkene acyl chlorides is added in above-mentioned reaction solution, is warming up to 75 DEG C, after reacting 8h, is down to room temperature, is centrifuged, is obtained 4- (3- benzene first
Acylthioureas base) phenyl acrylate, is washed 3 times with 300g absolute ethyl alcohols, 60 DEG C of vacuum drying 10h, obtains 4- (3- benzoyls
Base ghiourea group) phenylacrylic acid ester monomer；
B, 25 DEG C, 1.2L 150g/L acrylamide acetone soln is added in reactor, by 330g 4- piperidines first
Acid is added in reactor, is warming up to 60 DEG C, after reacting 7h, is down to room temperature, is centrifuged, is obtained N- acryloyl group -4- piperidines first
Acid amides, washed with 400g absolute ethyl alcohols, 40 DEG C of vacuum drying 10h, obtain N- acryloyl group -4- piperidine formyl amine monomers；
C, 25 DEG C, by obtained 4- in 0.6L 150g/L step a (3- benzoylthioureas base) phenyl acrylate list
The DMF solution of body adds 2L reactors, adds obtained N- acryloyls in 0.6L 180g/L step b
The DMF solution of base -4- piperidine formyl amine monomers, after mixing, 13g ABVNs are added into reactor,
55 DEG C of microwave radiation technologies react 30min, microwave power 400W, room temperature are cooled to after reaction, add 320g to enter absolute ethyl alcohol, stir
After 40min, centrifuge, obtain thiocarbamide analog copolymer heat stabilizer, washed 3 times with 240g absolute ethyl alcohols, 80 DEG C of vacuum drying
10h, obtain thiocarbamide analog copolymer heat stabilizer.
The Congo red heat-stable time Ts of the thiocarbamide analog copolymer heat stabilizer is 28min.
Embodiment 4：
A, 25 DEG C, 1.2L 260g/L ammonium thiocyanate acetone soln is added in reactor, by 140g benzene first in 0.5h
Acyl chlorides is added in reactor, after 25 DEG C of reaction 2h, is centrifuged, is obtained benzoyl isothiocyanate acetone mixture, will
115g para-aminophenol is added in above-mentioned benzoyl isothiocyanate acetone mixture, is warming up to 60 DEG C, 5h is reacted, by 98g
Acryloyl chloride is added in above-mentioned reaction solution, is warming up to 70 DEG C, after reacting 8h, is down to room temperature, is centrifuged, is obtained 4- (3- benzene
Formoxyl ghiourea group) phenyl acrylate, is washed 3 times with 450g absolute ethyl alcohols, 60 DEG C of vacuum drying 10h, obtains 4- (3- benzene first
Acylthioureas base) phenylacrylic acid ester monomer；
B, 25 DEG C, 1.2L 200g/L acrylamide acetone soln is added in reactor, by 440g 4- piperidines first
Acid is added in reactor, is warming up to 80 DEG C, after reacting 9h, is down to room temperature, is centrifuged, is obtained N- acryloyl group -4- piperidines first
Acid amides, washed with 500g absolute ethyl alcohols, 40 DEG C of vacuum drying 10h, obtain N- acryloyl group -4- piperidine formyl amine monomers；
C, 25 DEG C, by obtained 4- in 0.6L 260g/L step a (3- benzoylthioureas base) phenyl acrylate list
The DMF solution of body adds 2L reactors, adds obtained N- acryloyls in 0.6L 290g/L step b
The DMF solution of base -4- piperidine formyl amine monomers, after mixing, 20g ABVNs are added into reactor,
65 DEG C of microwave radiation technologies react 25min, microwave power 900W, and room temperature is cooled to after reaction, add 400g absolute methanols, stirring
After 50min, centrifuge, obtain thiocarbamide analog copolymer heat stabilizer, washed 3 times with 380g absolute methanols, 80 DEG C of vacuum drying
10h, obtain thiocarbamide analog copolymer heat stabilizer.
The Congo red heat-stable time Ts of the thiocarbamide analog copolymer heat stabilizer is 36min.
Embodiment 5：
A, 25 DEG C, 1.2L 135g/L ammonium thiocyanate acetone soln is added in reactor, by 130g benzoyls in 1h
Chlorine is added in reactor, after 25 DEG C of reaction 2h, is centrifuged, benzoyl isothiocyanate acetone mixture is obtained, by 109g
Para-aminophenol is added in above-mentioned benzoyl isothiocyanate acetone mixture, is warming up to 50 DEG C, 6h is reacted, by 96g propylene
Acyl chlorides is added in above-mentioned reaction solution, is warming up to 80 DEG C, after reacting 8h, is down to room temperature, is centrifuged, is obtained 4- (3- benzoyls
Base ghiourea group) phenyl acrylate, is washed 3 times with 430g absolute ethyl alcohols, 60 DEG C of vacuum drying 10h, obtains 4- (3- benzoyls
Ghiourea group) phenylacrylic acid ester monomer；
B, 25 DEG C, 1.2L 150g/L acrylamide acetone soln is added in reactor, by 295g 3- pyrrolidines
Formic acid is added in reactor, is warming up to 60 DEG C, after reacting 7h, is down to room temperature, is centrifuged, is obtained N- acryloyl group -3- pyrroles
Alkane formamide, washed with 380g absolute ethyl alcohols, 40 DEG C of vacuum drying 10h, obtain N- acryloyl group -3- pyrrolidine formamide lists
Body；
C, 25 DEG C, by obtained 4- in 0.6L 150g/L step a (3- benzoylthioureas base) phenyl acrylate list
The DMF solution of body adds 2L reactors, adds obtained N- acryloyls in 0.6L 200g/L step b
The DMF solution of base -3- pyrrolidine formyl amine monomers, after mixing, 15g ABVNs are added and reacted
Kettle, 55 DEG C of microwave radiation technologies react 20min, microwave power 800W, room temperature are cooled to after reaction, add 400g absolute ethyl alcohols, stir
After mixing 45min, centrifuge, obtain thiocarbamide analog copolymer heat stabilizer, washed 3 times with 350g absolute ethyl alcohols, 80 DEG C of vacuum are done
Dry 10h, obtain thiocarbamide analog copolymer heat stabilizer.
The Congo red heat-stable time Ts of the thiocarbamide analog copolymer heat stabilizer is 35min.
Embodiment 6：
A, 25 DEG C, 1.2L 140g/L ammonium thiocyanate acetone soln is added in reactor, by 120g benzoyls in 1h
Chlorine is added in reactor, after 25 DEG C of reaction 1.5h, is centrifuged, is obtained benzoyl isothiocyanate acetone mixture, will
102g para-aminophenol is added in above-mentioned benzoyl isothiocyanate acetone mixture, is warming up to 55 DEG C, 6h is reacted, by 86g
Acryloyl chloride is added in above-mentioned reaction solution, is warming up to 75 DEG C, after reacting 7h, is down to room temperature, is centrifuged, is obtained 4- (3- benzene
Formoxyl ghiourea group) phenyl acrylate, is washed 3 times with 400g absolute ethyl alcohols, 60 DEG C of dry 10h, obtains 4- (3- benzoyls
Ghiourea group) phenylacrylic acid ester monomer；
B, 25 DEG C, 1.2L 200g/L acrylamide acetone soln is added in reactor, by 390g 3- pyrrolidines
Formic acid is added in reactor, is warming up to 80 DEG C, after reacting 9h, is down to room temperature, is centrifuged, is obtained N- acryloyl group -3- pyrroles
Alkane formamide, washed with 550g absolute ethyl alcohols, 40 DEG C of vacuum drying 10h, obtain N- acryloyl group -3- pyrrolidine formamide lists
Body；
C, 25 DEG C, by obtained 4- in 0.6L 260g/L step a (3- benzoylthioureas base) phenyl acrylate list
The DMF solution of body adds 2L reactors, adds obtained N- acryloyls in 0.6L 280g/L step b
The DMF solution of base -3- pyrrolidine formyl amine monomers, after mixing, 30g azo-bis-iso-dimethyls are added
Enter reactor, 70 DEG C of microwave radiation technologies react 30min, microwave power 600W, room temperature is cooled to after reaction, add 500g without water beetle
Alcohol, after stirring 50min, centrifuge, obtain thiocarbamide analog copolymer heat stabilizer, washed 3 times with 400g absolute methanols, 80 DEG C true
Sky dries 10h, obtains thiocarbamide analog copolymer heat stabilizer.
The Congo red heat-stable time Ts of the thiocarbamide analog copolymer heat stabilizer is 40min.
Claims (10)
1. a kind of thiocarbamide analog copolymer heat stabilizer, it is characterised in that heat stabilizer is by 4- (3- benzoylthioureas base) phenyl
Acrylate monomer and acrylamide N Hete rocyclic derivatives monomers are made by free radicals copolymerization reaction, and its general structure is：
Wherein, R isIn one kind, degree of polymerization X is 300~500, and degree of polymerization Y is
600~1000.
A kind of 2. preparation method of thiocarbamide analog copolymer heat stabilizer as claimed in claim 1, it is characterised in that the preparation
Method is：
A, at room temperature, by concentration be 100~150g/L ammonium thiocyanate acetone soln be added in reactor, by chlorobenzoyl chloride with
Ammonium thiocyanate mass ratio is：0.5：1~1:1, chlorobenzoyl chloride is added in reactor, after room temperature reaction, centrifuges, obtains
Benzoyl isothiocyanate acetone mixture, it is 0.7 by para-aminophenol and chlorobenzoyl chloride mass ratio：1~0.9:1, will be to ammonia
Base phenol is added in above-mentioned benzoyl isothiocyanate acetone mixture, heating, reaction, by acryloyl chloride and chlorobenzoyl chloride matter
Amount is than being 0.5：1~0.9:1, acryloyl chloride is added in above-mentioned reaction solution, after heating, reaction, is down to room temperature, centrifugation point
From, 4- (3- benzoylthioureas base) phenyl acrylate is obtained, is washed with the absolute ethyl alcohol of 4~6 times of chlorobenzoyl chloride quality,
Vacuum drying, obtains 4- (3- benzoylthioureas base) phenylacrylic acid ester monomer；
B, at room temperature, the acrylamide acetone soln that concentration is 150~200g/L is added in reactor, by N heterocyclic formics
It is 1 with acrylamide mol ratio:1~2:1, N heterocyclic formics are added in reactor, after heating, reaction, room temperature is down to, centrifuges
Separation, obtains acrylamide N Hete rocyclic derivatives, is washed with the absolute ethyl alcohol of 2~4 times of acrylamide quality, vacuum drying, obtains
To acrylamide N Hete rocyclic derivatives monomers；
C, at room temperature, it is obtained 4- (3- benzoylthioureas base) phenylacrylic acid in 150~260g/L step a by concentration
The DMF solution of ester monomer adds reactor, by acrylamide N Hete rocyclic derivatives monomer and 4- (3- benzoyls
Base ghiourea group) phenyl acrylate monomer mole ratio be 1：1~3:1, add in the step b that concentration is 150~300g/L and be made
Acrylamide N Hete rocyclic derivatives monomers DMF solution, after mixing, by azo-initiator and 4- (3-
Benzoylthioureas base) phenyl acrylate monomer weight ratio be 0.005:1~0.2:1, azo-initiator is added and reacted
Kettle, microwave radiation technology reaction, is cooled to room temperature, by anhydrous alcohols solvent and 4- (3- benzoylthioureas base) phenylpropen after reaction
The mass ratio of acid ester monomer is 2:1~5:1, anhydrous alcohols solvent is added, after stirring 30~50min, centrifuges, is polymerize
Thing heat stabilizer, washed with the anhydrous alcohols solvent of 2~3 times of 4- (3- benzoylthioureas base) phenyl acrylate monomer mass
Wash, be dried in vacuo, obtain thiocarbamide analog copolymer heat stabilizer.
3. the preparation method of thiocarbamide analog copolymer heat stabilizer according to claim 2, it is characterised in that described in step a
Para-aminophenol is added in above-mentioned benzoyl isothiocyanate acetone mixture, temperature reaction, its temperature be 40~60
DEG C, the reaction time is 3~6h；
Described adds acryloyl chloride in above-mentioned reaction solution, temperature reaction, and its temperature is 70~85 DEG C, the reaction time 6
~8h.
4. the preparation method of thiocarbamide analog copolymer heat stabilizer according to claim 2, it is characterised in that described in step a
Vacuum drying, its temperature be 50~60 DEG C, the time is 8~10h.
5. the preparation method of thiocarbamide analog copolymer heat stabilizer according to claim 2, it is characterised in that described in step b
N heterocyclic formics be N- piperazinecarboxylic acids, 3- pyrrolidinecarboxylic acids, one kind in 4- piperidinecarboxylic acids.
6. the preparation method of thiocarbamide analog copolymer heat stabilizer according to claim 2, it is characterised in that by N in step b
Heterocyclic formic is added in reactor, temperature reaction, and its temperature is 60~80 DEG C, and the time is 7~9h；Described vacuum drying, its
Temperature is 40~50 DEG C, and the time is 8~10h.
7. the preparation method of thiocarbamide analog copolymer heat stabilizer according to claim 2, it is characterised in that described in step c
Azo-initiator be ABVN or azo-bis-iso-dimethyl.
8. the preparation method of thiocarbamide analog copolymer heat stabilizer according to claim 2, it is characterised in that described in step c
Anhydrous alcohols solvent be absolute methanol or absolute ethyl alcohol.
9. the preparation method of thiocarbamide analog copolymer heat stabilizer according to claim 2, it is characterised in that described in step c
Azo-initiator adds to reactor, microwave radiation technology reaction, its reaction temperature is 55~80 DEG C, the reaction time is 15~
30min。
10. the preparation method of thiocarbamide analog copolymer heat stabilizer according to claim 2, it is characterised in that institute in step c
The vacuum drying temperature stated is 60~80 DEG C, and the time is 8~10h.
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| WO2019007165A1 (en) * | 2017-07-03 | 2019-01-10 | 东南大学 | Thiourea copolymer heat stabilizer and preparation method therefor |
| CN113604027A (en) * | 2021-08-19 | 2021-11-05 | 广东工业大学 | Composite heat stabilizer and PVC product thereof |
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| CN112946157B (en) * | 2021-02-08 | 2023-10-27 | 武汉轻工大学 | Application of fluorescent thiourea derivatization reagent in detection of 3-chloro-1, 2-propanediol |
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