CN108530681A - A method of improving epoxidized methyl acetorieinoleate plasticizer and polyvinyl chloride resin compatibility - Google Patents
A method of improving epoxidized methyl acetorieinoleate plasticizer and polyvinyl chloride resin compatibility Download PDFInfo
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- CN108530681A CN108530681A CN201810061959.4A CN201810061959A CN108530681A CN 108530681 A CN108530681 A CN 108530681A CN 201810061959 A CN201810061959 A CN 201810061959A CN 108530681 A CN108530681 A CN 108530681A
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- acid
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- polyvinyl chloride
- chloride resin
- plasticizer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
- C07D301/16—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof formed in situ, e.g. from carboxylic acids and hydrogen peroxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
Abstract
The invention discloses a kind of methods improving epoxidized methyl acetorieinoleate plasticizer and polyvinyl chloride resin compatibility.The method is characterized in that the chlorine atom containing certain amount in used acetylation reagent; it is remarkably improved the compatibility of epoxidized methyl acetorieinoleate plasticizer and the polyvinyl chloride resin containing chlorine; and then the resistance to migration of plasticizer is improved, improve the flexibility and durability of PVC products.Plasticizer asepsis environment-protecting obtained in this way, can replace or part replaces phthalic ester plasticizer for the manufacture of the products such as artificial polyvinyl chloride leather, food packaging, medical equipment, and application prospect is extensive.
Description
Technical field
The present invention relates to a kind of methods improving epoxidized methyl acetorieinoleate plasticizer and polyvinyl chloride resin compatibility, belong to
In auxiliary chemicals field.
Background technology
Polyvinyl chloride (PVC) resin is the high polymer containing a large amount of polarity chlorine atoms generated by polymerization of vinyl choride monomer.
Due to the dipole-dipole interaction of chlorine atom, cause PVC intermolecular forces very big.If do not added plasticizer, polyvinyl chloride resin
It is in glassy state at room temperature, it is difficult to process and product performance is poor.Therefore, need addition certain in polyvinyl chloride resin process
The plasticizer of amount.Plasticizer molecule can penetrate into PVC interchains, shield in PVC and interact between chlorine atom, increase PVC interchains
Away from reduction PVC intermolecular forces make PVC be in rubbery state in use temperature range, improve its processing performance and usability
Energy.
In view of traditional phthalic ester plasticizer have carcinogenic risk and class female hormone effect, at present Europe, the United States,
Deng developed countries have been prohibited from using instead various environment-friendlyplasticizer plasticizers.Castor oil is as four big non-edible plants
One of object oil, modified product epoxidized methyl acetorieinoleate plasticizer has asepsis environment-protecting, degradable, thermal stability is good etc.
Advantage is mainly used in the industries such as senior engineering plastic, rubber, medical equipment.However, since methyl acetylricinolate exists
Acetyl group branch, this can reduce the compatibility of plasticizer itself and polyvinyl chloride resin, cause that plasticization temperature is higher, PVC finished product pliabilitys
The problems such as not good enough.
Invention content
The purpose of the invention is to overcome shortcoming and defect of the existing technology, and provide a kind of raising epoxy acetyl
The method of methyl ricinolcic acid plasticizer and polyvinyl chloride resin compatibility, it is characterised in that the processing step and condition of this method are as follows,
The number of material used is parts by weight：
(1) acetylization reaction：By 100 parts of methyl ricinolcic acid, 0-48 parts of solvent, 0-33 parts of acid binding agent is uniformly mixed, in 0- 40
DEG C, under nitrogen atmosphere, be added chloroacetylated reagent 36-77 parts into reactant, 0-3 parts of catalyst, then in 65 DEG C of 10-
Reaction 2-12 hours is added 0-400 parts of ice water washings, then uses the weak caustic solution and distilled water of 1.5-3% respectively after reaction
Organic layer is washed, until washing out water pH=5.5-6, water is removed in then vacuum distillation, obtains methyl acetylricinolate；
(2) epoxidation reaction：40-50 parts of 30% hydrogen peroxide, 15-20 parts of active oxygen carrier, 0.5-1 parts of the concentrated sulfuric acid is taken to be uniformly mixed
Peroxy acid is made, under the conditions of 40-48 DEG C, peroxy acid is added dropwise to 100 parts of methyl acetylricinolates and 25-35 parts of solvents
In mixture, then time for adding 30-90min reacts 3-5 hours at 45-48 DEG C, separates lower layer's acid after reaction, will be upper
Layer organic layer uses 1.5-3% weak caustic solutions and distillation water washing respectively, until washing out water pH=5.5-6, water is removed in then vacuum distillation,
Obtain epoxidized methyl acetorieinoleate.
Solvent in above method described in step (1) is chloroform, dichloroethanes, toluene, benzene, one kind in pyridine or more
Kind.
Acid binding agent in above method described in step (1) is one or more in pyridine, triethylamine.
Chloroacetylated reagent in above method described in step (1) is chloroacetic acid acid anhydride, dichloroacetic acid acid anhydride, trichloroacetic acid
It is one or more in acid anhydride, monochloro-acetyl chloride, dichloroacetyl chloride, trichloro-acetic chloride.
Catalyst in above method described in step (1) is phosphoric acid, niter cake, the concentrated sulfuric acid, benzene sulfonic acid, p-methyl benzenesulfonic acid
In it is one or more.
Weak caustic solution in above method described in step (1) is sodium carbonate liquor, one kind in sodium bicarbonate solution or more
Kind.
Active oxygen carrier in above method described in step (2) is one or more in formic acid, acetic acid.
Solvent in above method described in step (2) is one or more in benzene, toluene.
Weak caustic solution in above method described in step (2) is sodium carbonate liquor, one kind in sodium bicarbonate solution or more
Kind.
Compared with prior art, the present invention having the positive effect that：
(1) different number of chlorine atom is carried on the acetylation reagent that the present invention uses, according to similar compatibility principle, this will be notable
The compatibility of epoxidized methyl acetorieinoleate plasticizer and the polyvinyl chloride resin containing chlorine is improved, plasticized paste is easier during plasticising
Homogeneous mixed system is formed, to reduce plasticization temperature, improves polyvinyl chloride resin processing performance, improves product flexibility.
(2) at the same time, since the compatibility of epoxidized methyl acetorieinoleate plasticizer and polyvinyl chloride resin improves, this will
Plasticizer molecule is limited in the locomotivity of PVC interchains, and then the resistance to migration of plasticizer is significantly improved, greatly improves PVC systems
The durability and service life of product.
Description of the drawings
Fig. 1 is the synthetic route of epoxidized methyl acetorieinoleate plasticizer according to the present invention.
Specific implementation mode
The present invention is specifically described below by embodiment, is served only for that invention is further explained, no
It can be interpreted as limiting the scope of the present invention, the technician in the field can be according to the content of foregoing invention to the present invention
Make some nonessential modifications and adaptations.
Embodiment 1：
(1) under 40 DEG C, nitrogen atmosphere, 36 parts of the addition chloroacetic acid acid anhydride into 100 parts of methyl ricinolcic acids, 2 parts of phosphoric acid, then
2 hours are reacted at 65 DEG C, after reaction the sodium carbonate liquor and distillation water washing organic layer with 1.5% respectively, to wash-off water
PH=5.5, then vacuum distillation remove water, obtain methyl acetylricinolate；
(2) 40 parts of 30% hydrogen peroxide is taken, 15 parts of formic acid, 0.5 part of the concentrated sulfuric acid is uniformly mixed obtained peroxy acid, under the conditions of 40 DEG C,
Peroxy acid is added dropwise in the mixture of 100 parts of methyl acetylricinolates and 25 parts of benzene, time for adding 30min, then 45
DEG C reaction 3 hours, separate after reaction lower layer acid, by upper organic layer respectively with 1.5% sodium carbonate liquor and distilled water
Washing, until washing out water pH=5.5, water is removed in then vacuum distillation, obtains epoxidized methyl acetorieinoleate.
The epoxidized methyl acetorieinoleate prepared using above method, after measured chlorinity 8.9%, epoxide number 4.6%.
Plasticizing efficiency experiment shows plasticizer：PVC is 0.6:When 1 (weight ratio), can make PVC glass transition temperatures be reduced to from 87 DEG C-
30 DEG C, plasticizing efficiency 1.08.Compatibility experiments (solution temperature method) show PVC in common epoxidized methyl acetorieinoleate
In solution temperature be about 130 DEG C, and the solution temperature in the epoxidized methyl acetorieinoleate made from embodiment 1 is
120 DEG C, compatibility is substantially improved.Resistance to migration experiment shows the PVC films after common epoxidized methyl acetorieinoleate plasticising
In 70 DEG C, mass loss (mobility) about 1.8% in 24 hours, and epoxidized methyl acetorieinoleate made from embodiment 1 increases
Mass loss (mobility) ＜ 0.72% of plastic film under the same conditions.
Embodiment 2：
(1) under 40 DEG C, nitrogen atmosphere, 60 parts of chloroacetic acid acid anhydride, p-methyl benzenesulfonic acid 3 are added into 100 parts of methyl ricinolcic acids
Part, then react 4 hours at 65 DEG C, uses 1.5% sodium bicarbonate solution respectively after reaction and distill water washing organic layer,
To water pH=6 is washed out, water is removed in then vacuum distillation, obtains methyl acetylricinolate；
(2) 45 parts of 30% hydrogen peroxide is taken, 18 parts of formic acid, 0.8 part of the concentrated sulfuric acid is uniformly mixed obtained peroxy acid, under the conditions of 45 DEG C,
Peroxy acid is added dropwise in the mixture of 100 parts of methyl acetylricinolates and 30 parts of toluene, then time for adding 60min exists
45 DEG C are reacted 4 hours, lower layer's acid are separated after reaction, by upper organic layer respectively with 2% sodium bicarbonate solution and distilled water
Washing, until washing out water pH=6, water is removed in then vacuum distillation, obtains epoxidized methyl acetorieinoleate.
The epoxidized methyl acetorieinoleate prepared using above method, after measured chlorinity 14.7%, epoxide number
4.2%.Plasticizing efficiency experiment shows plasticizer：PVC is 0.6:When 1 (weight ratio), PVC glass transition temperatures can be made to be dropped from 87 DEG C
Down to -31 DEG C, plasticizing efficiency 1.10.Compatibility experiments (solution temperature method) show PVC in common epoxy acetylricinoleate oleic acid
The solution temperature of methyl esters is about 130 DEG C, and the solution temperature in the epoxidized methyl acetorieinoleate made from embodiment 2 is
116 DEG C, compatibility is substantially improved.Resistance to migration experiment shows the PVC films after common epoxidized methyl acetorieinoleate plasticising
In 70 DEG C, mass loss (mobility) about 1.8% in 24 hours, and epoxidized methyl acetorieinoleate made from embodiment 2 increases
Mass loss (mobility) ＜ 0.37% of plastic film under the same conditions.
Embodiment 3：
(1) by 100 parts of methyl ricinolcic acid, 48 parts of chloroform is uniformly mixed, under 0 DEG C, nitrogen atmosphere, is added dropwise into reactant
Then the mixture of 80 parts of trichloro-acetic chlorides and 33 parts of pyridines reacts 12 hours at 10 DEG C, 400 portions of ice water is added after reaction
Washing, then with respectively use 3% sodium bicarbonate solution and distill water washing organic layer, until wash-off water pH=6, be then evaporated under reduced pressure
Water is removed, methyl acetylricinolate is obtained；
(2) 50 parts of 30% hydrogen peroxide is taken, 20 parts of acetic acid, 1 part of the concentrated sulfuric acid is uniformly mixed obtained peroxy acid, will under the conditions of 48 DEG C
Peroxy acid is added dropwise in the mixture of 100 parts of methyl acetylricinolates and 35 parts of benzene, time for adding 90min, then at 48 DEG C
Reaction 5 hours separates lower layer's acid after reaction, and upper organic layer with 3% sodium bicarbonate solution and is distilled water washing respectively,
To water pH=6 is washed out, water is removed in then vacuum distillation, obtains epoxidized methyl acetorieinoleate.
The epoxidized methyl acetorieinoleate prepared using above method, after measured chlorinity 20.5%, epoxide number
4.0%.Plasticizing efficiency experiment shows plasticizer：PVC is 0.6:When 1 (weight ratio), PVC glass transition temperatures can be made to be dropped from 87 DEG C
Down to -19 DEG C, plasticizing efficiency 0.98.Compatibility experiments (solution temperature method) show PVC in common epoxy acetylricinoleate oleic acid
The solution temperature of methyl esters is about 130 DEG C, and the solution temperature in the epoxidized methyl acetorieinoleate made from embodiment 3 is
110 DEG C, compatibility is substantially improved.Resistance to migration experiment shows the PVC films after common epoxidized methyl acetorieinoleate plasticising
In 70 DEG C, mass loss (mobility) about 1.8% in 24 hours, and epoxidized methyl acetorieinoleate made from embodiment 3 increases
Mass loss (mobility) ＜ 0.19% of plastic film under the same conditions.
Claims (9)
1. a kind of method improving epoxidized methyl acetorieinoleate plasticizer and polyvinyl chloride resin compatibility, it is characterised in that the party
The processing step and condition of method are as follows, and the number of material used is parts by weight：
Acetylization reaction：By 100 parts of methyl ricinolcic acid, 0-48 parts of solvent, 0-33 parts of acid binding agent is uniformly mixed, 0-40 DEG C,
Under nitrogen atmosphere, chloroacetylated reagent 36-80 parts are added into reactant, then 0-3 parts of catalyst is reacted at 10-65 DEG C
2-12 hours, 0-400 parts of ice water washings are added after reaction, then have respectively with the weak caustic solution of 1.5-3% and distillation water washing
Machine layer, until washing out water pH=5.5-6, water is removed in then vacuum distillation, obtains methyl acetylricinolate；
（2）Epoxidation reaction：40-50 parts of 30% hydrogen peroxide, 15-20 parts of active oxygen carrier, 0.5-1 parts of the concentrated sulfuric acid is taken to be uniformly mixed
Peroxy acid is made, under the conditions of 40-48 DEG C, peroxy acid is added dropwise to 100 parts of methyl acetylricinolates and 25-35 parts of solvents
In mixture, then time for adding 30-90min reacts 3-5 hours at 45-48 DEG C, separates lower layer's acid after reaction, will be upper
Layer organic layer uses 1.5-3% weak caustic solutions and distillation water washing respectively, until washing out water pH=5.5-6, water is removed in then vacuum distillation, obtains
To epoxidized methyl acetorieinoleate.
2. a kind of raising epoxidized methyl acetorieinoleate plasticizer according to claim 1 and polyvinyl chloride resin compatibility
Method, it is characterised in that step（1）The solvent is one or more in chloroform, dichloroethanes, toluene, benzene, pyridine.
3. a kind of raising epoxidized methyl acetorieinoleate plasticizer according to claim 1 and polyvinyl chloride resin compatibility
Method, it is characterised in that step（1）The acid binding agent is one or more in pyridine, triethylamine.
4. a kind of raising epoxidized methyl acetorieinoleate plasticizer according to claim 1 and polyvinyl chloride resin compatibility
Method, it is characterised in that step（1）The chloroacetylated reagent is chloroacetic acid acid anhydride, dichloroacetic acid acid anhydride, Trichloroacetic anhydride, one
It is one or more in chloracetyl chloride, dichloroacetyl chloride, trichloro-acetic chloride.
5. a kind of raising epoxidized methyl acetorieinoleate plasticizer according to claim 1 and polyvinyl chloride resin compatibility
Method, it is characterised in that step（1）The catalyst is in phosphoric acid, niter cake, the concentrated sulfuric acid, benzene sulfonic acid, p-methyl benzenesulfonic acid
It is one or more.
6. a kind of raising epoxidized methyl acetorieinoleate plasticizer according to claim 1 and polyvinyl chloride resin compatibility
Method, it is characterised in that step（1）The weak caustic solution is one or more in sodium carbonate liquor, sodium bicarbonate solution.
7. a kind of raising epoxidized methyl acetorieinoleate plasticizer according to claim 1 and polyvinyl chloride resin compatibility
Method, it is characterised in that step（2）The active oxygen carrier is one or more in formic acid, acetic acid.
8. a kind of raising epoxidized methyl acetorieinoleate plasticizer according to claim 1 and polyvinyl chloride resin compatibility
Method, it is characterised in that step（2）The solvent is one or more in benzene, toluene.
9. a kind of raising epoxidized methyl acetorieinoleate plasticizer according to claim 1 and polyvinyl chloride resin compatibility
Method, it is characterised in that step（2）The weak caustic solution is one or more in sodium carbonate liquor, sodium bicarbonate solution.
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Cited By (2)
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| CN110951055A (en) * | 2019-12-31 | 2020-04-03 | 江南大学 | Method for preparing environment-friendly plasticizer by using biological fermentation product lactic acid and application thereof |
| CN111500075A (en) * | 2020-05-27 | 2020-08-07 | 山东华跃新材料科技有限责任公司 | Novel environment-friendly plasticizer |
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