CN107200957A - A kind of method of epoxy aliphatic acid methyl ester resistance to migration in raising flexible PVC - Google Patents
A kind of method of epoxy aliphatic acid methyl ester resistance to migration in raising flexible PVC Download PDFInfo
- Publication number
- CN107200957A CN107200957A CN201710419660.7A CN201710419660A CN107200957A CN 107200957 A CN107200957 A CN 107200957A CN 201710419660 A CN201710419660 A CN 201710419660A CN 107200957 A CN107200957 A CN 107200957A
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- Prior art keywords
- pvc
- acid methyl
- methyl ester
- aliphatic acid
- epoxy aliphatic
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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
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a kind of method for improving epoxy aliphatic acid methyl ester resistance to migration in flexible PVC, in the co-mixing system that modified activated Calcium carbonate is added to PVC and epoxy aliphatic acid methyl ester, pass through mixed at high speed, epoxy aliphatic acid methyl ester is easily combined with the surface of activated Calcium carbonate by unsaturated bond, and activated Calcium carbonate is stablized relatively in the polymer, it is restricted the motion of the strand of epoxy aliphatic acid methyl ester, and then its migration in PVC is inhibited, this method can effectively improve the service life and physiological safety performance of PVC product.
Description
Technical field
The present invention relates to epoxy fatty acid methyl in polyvinyl chloride processing technique field, more particularly to a kind of raising flexible PVC
The method of ester resistance to migration.
Background technology
Polyvinyl chloride (PVC) is one of five big general-purpose plastics, applied to fields such as artificial leather, cable, toy, footwear materials,
Purposes is wide, and consumption is big, but polyvinyl chloride Interchain interaction power it is big, it is necessary to add in process a large amount of plasticizer with
Macromolecular chain interphase interaction is reduced, the purpose for improving processing characteristics, softening product is reached.Conventional plasticizer has adjacent benzene at present
Diformic ester, citric acid ester type, polyesters and epoxyfatty acid esters, wherein phthalic ester plasticizer performance are most
Good, consumption is maximum, but because of its physiological-toxicity, is disabled or limited the use of by developed countries such as Europe, the United States；Citric acid ester plasticizer environment
Close friend, but flash-point is relatively low, and plasticizing efficiency is poor；And epoxyfatty acid esters are the green increasings based on natural animal-plant oil modification
Mould agent, with it is cheap, nontoxic, environment-friendly the characteristics of, it is considered to be the preferable replacement of phthalic ester plasticizer
Product, but epoxyfatty acid esters plasticizer resistance to migration is poor, and its further genralrlization uses also restrained.
《Inhibitory action of the CaCO3 particles to the migration of plasticizer in PVC membrane materials》In one text by using nano active and
Hyper fine CaCO3 suppresses migration of plasticizer in PVC composite film materials, utilizes thermal oxide, SEM, universal material testing
Machine is tested composite membrane, influence of the analysis addition CaCO3 particles to the mechanical property of composite film material.As a result show,
CaCO3 particles can effectively suppress the precipitation of plasticizer in composite membrane.During yet with adding calcium carbonate particle in the base, easily
Flock together, reduce the resistance to migration of plasticiser, while can also be affected to PVC mechanical property, this is just
Need to add the modified inorganic particulate in surface by process modification, there can be good dispersiveness in PVC matrix, suppress
Migration of plasticizer, while PVC mechanical property will not be reduced.
The content of the invention
The object of the invention is exactly to improve epoxyfatty acid in flexible PVC there is provided one kind to make up the defect of prior art
The method of methyl esters resistance to migration.
The present invention is achieved by the following technical solutions：
A kind of method of epoxy aliphatic acid methyl ester resistance to migration in raising flexible PVC, including step in detail below：
（1）Appropriate distilled water is added in three-necked flask, is placed in ultrasonator, 60-65 DEG C, addition is heated to
Appropriate titanate coupling agent TC-F is stand-by；
（2）The amount anhydrous calcium chloride of same substance and ammonium carbonate are dissolved in the distilled water of same volume, then with same constant speed
Degree is added drop-wise to step（1）In system, stirring reaction 30-40 minutes after completion of dropping, suction filtration after completion of the reaction, with distillation water washing
2-3 times, filter cake is dried in vacuo, obtains modified activated Calcium carbonate；
（3）The acetone that 2-2.5 times of total amount is measured is swollen in after PVC powder, PVC paste resin and epoxy aliphatic acid methyl ester are sufficiently mixed
In, then add step（2）Stirred 10-15 minutes in obtained product, feeding high-speed mixer, obtain PVC slurries, finally will
Different products are made in PVC slurries.
The method of epoxy aliphatic acid methyl ester resistance to migration, step in a kind of raising PVC（1）Described titanate coupling agent
TC-F addition is the 1.25% of anhydrous calcium chloride and ammonium carbonate total amount.
The method of epoxy aliphatic acid methyl ester resistance to migration, step in a kind of raising PVC（1）The work(of described ultrasonator
Rate is 250W.
The method of epoxy aliphatic acid methyl ester resistance to migration, step in a kind of raising PVC（2）Described mixing speed is 200-
300 revs/min.
The method of epoxy aliphatic acid methyl ester resistance to migration, step in a kind of raising PVC（3）Described high-speed mixer is stirred
Speed is mixed for 1000-1200 revs/min.
The method of epoxy aliphatic acid methyl ester resistance to migration, step in a kind of raising PVC（3）Described PVC powder, PVC paste tree
The mass ratio of fat, epoxy aliphatic acid methyl ester and modified activated Calcium carbonate is 5:5:5:3.
It is an advantage of the invention that：The present invention will synthesize integrated with modification, prepare nm-class active calcium carbonate, be stirred by machinery
Mix heating, ultrasonic wave added technique to be modified the titanate coupling agent TC-F surfaces for being used for nm-class active calcium carbonate, by rationally controlling
Mixing speed processed, reaction temperature, can reduce the secondary agglomeration of particle, generate the calcium carbonate of small particle, while strong shearing is made
With making in solution the increase of microcrystal grain impact energy, and then the not bery firm crystallite of absorption is set to scatter, so being difficult to form bulky grain
Crystal, be conducive to the generation of ultrafine particle.
Modified activated Calcium carbonate is added in the co-mixing system of PVC and epoxy aliphatic acid methyl ester by the present invention, passes through height
Speed mixing, epoxy aliphatic acid methyl ester is easily combined with the surface of activated Calcium carbonate by unsaturated bond, and activated Calcium carbonate is in polymerization
Stablize relatively in thing, be restricted the motion of the strand of epoxy aliphatic acid methyl ester, and then inhibit its moving in PVC
Move, this method can effectively improve the service life and physiological safety performance of PVC products.
Embodiment
A kind of method of epoxy aliphatic acid methyl ester resistance to migration in raising flexible PVC, including step in detail below：
（1）60mL distilled water is added in three-necked flask, is placed in ultrasonator, 60 DEG C are heated to and with 250W
Power ultrasonic state under to add 0.78g titanate coupling agents TC-F stand-by；
（2）0.3mol anhydrous calcium chloride and 0.3mol ammonium carbonate are dissolved in 600mL distilled water respectively, then with same
Uniform velocity is added drop-wise to step（1）In system, with 200 revs/min of speed stirring reaction 30 minutes after completion of dropping, after completion of the reaction
Suction filtration, with water washing is distilled 2 times, filter cake is dried in vacuo, modified activated Calcium carbonate is obtained；
（3）2 times of amounts of total amount are swollen in after 50gPVC powder, 50gPVC paste resins and 50g epoxy aliphatic acid methyl esters are sufficiently mixed
In acetone, step is then added（2）Stirred 10 minutes with 1000 revs/min of speed in obtained product, feeding high-speed mixer,
PVC slurries are obtained, PVC slurries are finally made to different products.
Claims (6)
1. a kind of method for improving epoxy aliphatic acid methyl ester resistance to migration in flexible PVC, it is characterised in that including walking in detail below
Suddenly：
（1）Appropriate distilled water is added in three-necked flask, is placed in ultrasonator, 60-65 DEG C, addition is heated to
Appropriate titanate coupling agent TC-F is stand-by；
（2）The amount anhydrous calcium chloride of same substance and ammonium carbonate are dissolved in the distilled water of same volume, then with same constant speed
Degree is added drop-wise to step（1）In system, stirring reaction 30-40 minutes after completion of dropping, suction filtration after completion of the reaction, with distillation water washing
2-3 times, filter cake is dried in vacuo, obtains modified activated Calcium carbonate；
（3）The acetone that 2-2.5 times of total amount is measured is swollen in after PVC powder, PVC paste resin and epoxy aliphatic acid methyl ester are sufficiently mixed
In, then add step（2）Stirred 10-15 minutes in obtained product, feeding high-speed mixer, obtain PVC slurries, finally will
Different products are made in PVC slurries.
2. according to claim 1 in a kind of raising PVC epoxy aliphatic acid methyl ester resistance to migration method, its feature exists
In step（1）Described titanate coupling agent TC-F addition is anhydrous calcium chloride and the 1.25-1.5% of ammonium carbonate total amount.
3. according to claim 1 in a kind of raising PVC epoxy aliphatic acid methyl ester resistance to migration method, its feature exists
In step（1）The power of described ultrasonator is 250W.
4. according to claim 1 in a kind of raising PVC epoxy aliphatic acid methyl ester resistance to migration method, its feature exists
In step（2）Described mixing speed is 200-300 revs/min.
5. according to claim 1 in a kind of raising PVC epoxy aliphatic acid methyl ester resistance to migration method, its feature exists
In step（3）The mixing speed of described high-speed mixer is 1000-1200 revs/min.
6. according to claim 1 in a kind of raising PVC epoxy aliphatic acid methyl ester resistance to migration method, its feature exists
In step（3）The mass ratio of activated Calcium carbonate of the described PVC powder, PVC paste resin, epoxy aliphatic acid methyl ester with being modified is 5:
5:5:3。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710419660.7A CN107200957A (en) | 2017-06-06 | 2017-06-06 | A kind of method of epoxy aliphatic acid methyl ester resistance to migration in raising flexible PVC |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710419660.7A CN107200957A (en) | 2017-06-06 | 2017-06-06 | A kind of method of epoxy aliphatic acid methyl ester resistance to migration in raising flexible PVC |
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| Publication Number | Publication Date |
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| CN107200957A true CN107200957A (en) | 2017-09-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201710419660.7A Pending CN107200957A (en) | 2017-06-06 | 2017-06-06 | A kind of method of epoxy aliphatic acid methyl ester resistance to migration in raising flexible PVC |
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| Country | Link |
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| CN (1) | CN107200957A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966497A (en) * | 2006-09-11 | 2007-05-23 | 罗春妹 | Epoxy fatty acid methyl ester |
| CN103834128A (en) * | 2014-02-26 | 2014-06-04 | 四川大学 | Method of improving mobility resistance of plasticizer in artificial leather and preparation method of modified polyvinyl chloride used in method |
| CN105255061A (en) * | 2015-11-16 | 2016-01-20 | 广东达华节水科技股份有限公司 | Environment-friendly soft PVC plasticizer |
-
2017
- 2017-06-06 CN CN201710419660.7A patent/CN107200957A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966497A (en) * | 2006-09-11 | 2007-05-23 | 罗春妹 | Epoxy fatty acid methyl ester |
| CN103834128A (en) * | 2014-02-26 | 2014-06-04 | 四川大学 | Method of improving mobility resistance of plasticizer in artificial leather and preparation method of modified polyvinyl chloride used in method |
| CN105255061A (en) * | 2015-11-16 | 2016-01-20 | 广东达华节水科技股份有限公司 | Environment-friendly soft PVC plasticizer |
Non-Patent Citations (2)
| Title |
|---|
| 张斌等: ""CaCO3粒子对PVC膜材中增塑剂迁移的抑制作用"", 《稀有金属材料与工程》 * |
| 李树材等: ""纳米粒子抑制软质聚氯乙烯中增塑剂迁移的研究"", 《塑料科技》 * |
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Application publication date: 20170926 |
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