CN110885563A - PVC environment-friendly plasticizer and preparation method thereof - Google Patents
PVC environment-friendly plasticizer and preparation method thereof Download PDFInfo
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- CN110885563A CN110885563A CN201911060590.6A CN201911060590A CN110885563A CN 110885563 A CN110885563 A CN 110885563A CN 201911060590 A CN201911060590 A CN 201911060590A CN 110885563 A CN110885563 A CN 110885563A
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- 239000004014 plasticizer Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 46
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 23
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 19
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 19
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 13
- 150000004671 saturated fatty acids Chemical class 0.000 claims abstract description 12
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims abstract description 12
- JYKSTGLAIMQDRA-UHFFFAOYSA-N tetraglycerol Chemical compound OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO JYKSTGLAIMQDRA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000012424 soybean oil Nutrition 0.000 claims abstract description 10
- 239000003549 soybean oil Substances 0.000 claims abstract description 10
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 16
- 239000005639 Lauric acid Substances 0.000 claims description 8
- 238000007127 saponification reaction Methods 0.000 claims description 8
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 claims description 3
- 235000021360 Myristic acid Nutrition 0.000 claims description 3
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 claims description 3
- 235000021314 Palmitic acid Nutrition 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 235000003441 saturated fatty acids Nutrition 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 38
- 229920000915 polyvinyl chloride Polymers 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- 239000008037 PVC plasticizer Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 238000007551 Shore hardness test Methods 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- 239000006084 composite stabilizer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- -1 cyclic acetal Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000008029 phthalate plasticizer Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- 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
-
- 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
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
-
- 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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- 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
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- 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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- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a PVC environment-friendly plasticizer and a preparation method thereof. The PVC environment-friendly plasticizer is prepared from tetrapolyglycerol, saturated fatty acid, stannous octoate, acetic anhydride, epoxidized soybean oil and saponified rosin modified nano calcium carbonate, and the preparation method comprises the following steps: 1) adding the tetraglycerol, the saturated fatty acid and the stannous octoate into a reaction kettle, and fully reacting at the temperature of 150-160 ℃ under the condition of 10-20 mbar; 2) cooling the materials in the reaction kettle to 100-110 ℃, adding acetic anhydride, and fully reacting under normal pressure; 3) and cooling the materials in the reaction kettle to normal temperature, adding epoxidized soybean oil and saponified rosin modified nano calcium carbonate, and emulsifying. The plasticizer disclosed by the invention has the advantages of high plasticizing efficiency, good compatibility with PVC, good thermal stability, economy, environmental friendliness and the like, and is simple in preparation process and suitable for industrial popularization and application.
Description
Technical Field
The invention relates to a PVC environment-friendly plasticizer and a preparation method thereof, belonging to the technical field of plastic additives.
Background
The plasticizer is an additive with the largest dosage in polyvinyl chloride (PVC) materials, and makes an important contribution to the industrial application of PVC. The plasticizer mainly has the following two functions in the PVC material: firstly, the melting temperature and the melt viscosity of PVC are reduced, so that the processing temperature of the PVC is reduced; and secondly, the PVC product is endowed with flexibility, elasticity and low temperature resistance.
The plasticizer is various, and the phthalate plasticizer is most commonly used at present. However, as environmental awareness increases, toxicity of plasticizers is becoming more and more of a concern, and conventional phthalate-based plasticizers have been banned in many foreign countries due to the carcinogenic risk. Therefore, environmentally friendly plasticizers such as citric acid esters and epoxy compounds have been favored, but these plasticizers have low plasticizing efficiency and are difficult to use as primary plasticizers.
In recent years, researchers have developed some novel plasticizers, but all have significant drawbacks, such as: CN 105722906A discloses a plasticizer for polymers, which is a carboxylic acid (mainly C)12～C22Fatty acid) and hydroxyl-containing cyclic acetal or cyclic ketal, which does not involve environmental protection problems, but has low plasticizing efficiency and high manufacturing cost, and is difficult to industrially popularize and apply; CN 105061807A discloses a non-phthalic plasticizer which is pentaerythritol and C4～C5The ester formed by the reaction of the monocarboxylic acid(s) has high plasticizing efficiency, but has poor compatibility with PVC and is easy to precipitate.
Therefore, there is a need to develop a plasticizer which has high plasticizing efficiency, good compatibility with PVC, good thermal stability, economy and environmental protection.
Disclosure of Invention
The invention aims to provide a PVC environment-friendly plasticizer and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
the PVC environment-friendly plasticizer is prepared from the following raw materials in parts by mass:
tetraglycerol: 100 parts of (A);
saturated fatty acids: 30-60 parts;
stannous octoate: 1.5-2.5 parts;
acetic anhydride: 80-120 parts of a solvent;
epoxidized soybean oil: 20-30 parts of a solvent;
saponification rosin modified nano calcium carbonate: 3-8 parts.
Preferably, the saturated fatty acid is C12～C18The saturated fatty acid of (4).
More preferably, the saturated fatty acid is at least one of lauric acid, palmitic acid, myristic acid, and stearic acid.
Preferably, the average particle size of the saponified rosin modified nano calcium carbonate is 40-90 nm.
Preferably, the BET specific surface area of the saponified rosin modified nano calcium carbonate is 18-30 m2/g。
Preferably, the saponified rosin modified nano calcium carbonate is obtained by activating and modifying nano calcium carbonate by using rosin saponification liquid with the mass fraction of 3.0-4.5%.
The preparation method of the PVC environment-friendly plasticizer comprises the following steps:
1) adding the tetraglycerol, the saturated fatty acid and the stannous octoate into a reaction kettle, and fully reacting at the temperature of 150-160 ℃ under the condition of 10-20 mbar;
2) cooling the materials in the reaction kettle to 100-110 ℃, adding acetic anhydride, and fully reacting under normal pressure;
3) and cooling the materials in the reaction kettle to normal temperature, adding epoxidized soybean oil and saponified rosin modified nano calcium carbonate, and emulsifying to obtain the PVC environment-friendly plasticizer.
Preferably, the reaction time in the step 1) is 4-6 h.
Preferably, the reaction time in the step 2) is 1-1.5 h.
Preferably, the emulsifying time in the step 3) is 40-60 min.
The invention has the beneficial effects that: the plasticizer disclosed by the invention has the advantages of high plasticizing efficiency, good compatibility with PVC, good thermal stability, economy, environmental friendliness and the like, and is simple in preparation process and suitable for industrial popularization and application.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
the preparation method of the PVC environment-friendly plasticizer comprises the following steps:
1) adding 100 parts by mass of tetraglycerol, 30 parts by mass of lauric acid and 1.8 parts by mass of stannous octoate into a high-temperature high-pressure reaction kettle, and reacting for 5 hours at 155 ℃ under the condition of 15 mbar;
2) cooling the materials in the high-temperature high-pressure reaction kettle to 105 ℃, adding 115 parts by mass of acetic anhydride, and reacting for 1.2h under the normal pressure condition;
3) cooling the materials in the high-temperature high-pressure reaction kettle to normal temperature, transferring into an emulsifying machine, adding 20 parts by mass of epoxidized soybean oil and 4 parts by mass of saponified rosin-modified nano calcium carbonate (nano calcium carbonate with surface modified by rosin saponification solution with mass fraction of 3.5%, and specific surface area of 22 m)2And/g, the average particle size is 75nm), emulsifying for 40min, and obtaining the PVC environment-friendly plasticizer.
Example 2:
the preparation method of the PVC environment-friendly plasticizer comprises the following steps:
1) adding 100 parts by mass of tetraglycerol, 30 parts by mass of palmitic acid, 20 parts by mass of lauric acid and 2.5 parts by mass of stannous octoate into a high-temperature high-pressure reaction kettle, and reacting for 4.8 hours at the temperature of 150 ℃ and under the condition of 15 mbar;
2) cooling the materials in the high-temperature high-pressure reaction kettle to 105 ℃, adding 82 parts by mass of acetic anhydride, and reacting for 1 hour under the normal pressure condition;
3) cooling the materials in the high-temperature high-pressure reaction kettle to normal temperature and convertingAdding into emulsifying machine, adding 28 mass parts of epoxidized soybean oil and 6 mass parts of saponified rosin modified nano calcium carbonate (nano calcium carbonate with surface modified by rosin saponification solution with mass fraction of 3.0% and specific surface area of 18 m)2And/g, the average particle size is 85nm), emulsifying for 60min, and obtaining the PVC environment-friendly plasticizer.
Example 3:
the preparation method of the PVC environment-friendly plasticizer comprises the following steps:
1) adding 100 parts by mass of tetraglycerol, 20 parts by mass of stearic acid, 15 parts by mass of lauric acid, 5 parts by mass of myristic acid and 2 parts by mass of stannous octoate into a high-temperature high-pressure reaction kettle, and reacting for 6 hours at the temperature of 155 ℃ and under the condition of 12 mbar;
2) cooling the materials in the high-temperature high-pressure reaction kettle to 105 ℃, adding 96 parts by mass of acetic anhydride, and reacting for 1.2h under the normal pressure condition;
3) cooling the materials in the high-temperature high-pressure reaction kettle to normal temperature, transferring into an emulsifying machine, adding 24 parts by mass of epoxidized soybean oil and 3 parts by mass of saponified rosin-modified nano calcium carbonate (nano calcium carbonate with surface modified by 4.5% by mass of rosin saponification liquid and specific surface area of 28 m)2The average grain diameter is 60nm) and emulsifying for 60min to obtain the PVC environment-friendly plasticizer.
Example 4:
the preparation method of the PVC environment-friendly plasticizer comprises the following steps:
1) adding 100 parts by mass of tetraglycerol, 10 parts by mass of stearic acid, 45 parts by mass of lauric acid, 5 parts by mass of myristic acid and 2.5 parts by mass of stannous octoate into a high-temperature high-pressure reaction kettle, and reacting for 6 hours at the temperature of 155 ℃ and under the condition of 12 mbar;
2) cooling the materials in the high-temperature high-pressure reaction kettle to 105 ℃, adding 120 parts by mass of acetic anhydride, and reacting for 1.2h under the normal pressure condition;
3) cooling the materials in the high-temperature high-pressure reaction kettle to normal temperature, transferring into an emulsifying machine, adding 20 parts by mass of epoxidized soybean oil and 8 parts by mass of saponified rosin-modified nano calcium carbonate (nano calcium carbonate with surface modified by rosin saponification solution with mass fraction of 3.5%, and specific surface area of 20 m)2Per g, average particleThe diameter is 70nm), emulsifying for 40min to obtain the PVC environment-friendly plasticizer.
Comparative example 1:
the commercial PVC plasticizer DOP (dioctyl phthalate).
Comparative example 2:
a PVC plasticizer is prepared by the following steps:
adding 100 parts by mass of tetraglycerol, 30 parts by mass of lauric acid and 1.8 parts by mass of stannous octoate into a high-temperature high-pressure reaction kettle, and reacting for 5 hours at 155 ℃ under the condition of 15mbar to obtain the PVC plasticizer.
Comparative example 3:
a PVC plasticizer is prepared by the following steps:
1) adding 100 parts by mass of tetraglycerol, 30 parts by mass of lauric acid and 1.8 parts by mass of stannous octoate into a high-temperature high-pressure reaction kettle, and reacting for 5 hours at 155 ℃ under the condition of 15 mbar;
2) and cooling the materials in the high-temperature high-pressure reaction kettle to 105 ℃, adding 115 parts by mass of acetic anhydride, and reacting for 1.2h under the normal pressure condition to obtain the PVC plasticizer.
Test example:
1) the plasticizers of examples 1 to 4 and comparative examples 1 to 3 were subjected to thermal stability and compatibility tests, respectively, and the test results are shown in table 1:
table 1 thermal stability and compatibility test results for plasticizers
| Test index | Thermal stability time (min) | Dissolution temperature (. degree.C.) |
| Example 1 | 11.6 | 102 |
| Example 2 | 11.3 | 109 |
| Example 3 | 10.9 | 110 |
| Example 4 | 12.0 | 101 |
| Comparative example 1 | 8.8 | 131 |
| Comparative example 2 | 8.5 | 133 |
| Comparative example 3 | 9.8 | 126 |
Note:
thermal stability time: testing by using a Hapu rheometer, wherein the time corresponding to the rising inflection point of the plasticizing curve is the thermal stability time;
dissolution temperature: preparing suspension with the mass fraction of PVC (polyvinyl chloride) being 2% by using PVC resin and a plasticizer, adding the suspension into a glass test tube, heating the suspension by using an oil bath under shaking, controlling the temperature rise rate to be 5 ℃/min until the suspension becomes transparent, measuring the temperature at the moment to be the dissolution temperature of the PVC, wherein the lower the dissolution temperature is, the better the compatibility of the plasticizer and the PVC is represented.
As can be seen from Table 1: the thermal stability and compatibility of the PVC environment-friendly plasticizer are obviously superior to those of the plasticizers in comparative examples 1-3.
2) PVC sample strips are prepared from the plasticizers in the examples 1-4 and the comparative examples 1-3 according to the formula shown in the table 2, the PVC sample strips are marked as sample strips 1-4 and comparative sample strips 1-3, and then performance tests are carried out on the sample strips, wherein the test results are shown in the table 3:
TABLE 2 composition of PVC sample strips
| Raw materials | Mass portion of |
| PVC | 100 |
| Plasticizer | 32 |
| Ground calcium carbonate | 15 |
| Antioxidant 1076 | 0.3 |
| Calcium-zinc composite stabilizer | 3 |
TABLE 3 Performance test results for PVC splines
| Test index | Shore A hardness | Tg(℃) | Elongation at Break (%) |
| Sample bar 1 | 83 | 38.2 | 218 |
| Sample bar 2 | 85 | 40.7 | 198 |
| Sample No. 3 | 87 | 42.5 | 185 |
| Sample strip 4 | 82 | 37.6 | 224 |
| Comparative sample No. 1 | 91 | 50.8 | 162 |
| Comparison sample 2 | 92 | 51.2 | 153 |
| Comparison sample 3 | 88 | 48.7 | 171 |
Note:
shore A hardness: referring to a Shore hardness test method of GB 2411-80 plastics;
Tg(glass transition temperature): measuring by adopting a dynamic thermomechanical analysis (DMA) method, wherein the measuring temperature interval is-100-160 ℃, and the heating rate is 5 ℃/min;
elongation at break: refer to the general rule of GB/T1039-92 plastic mechanical property test method.
As can be seen from Table 3: after the PVC environment-friendly plasticizer is added into PVC, the PVC environment-friendly plasticizer has lower glass transition temperature, lower hardness and higher elongation, and the plasticizing effect of the PVC environment-friendly plasticizer is obviously better than that of the plasticizers in comparative examples 1-3.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The PVC environment-friendly plasticizer is characterized in that: the feed is prepared from the following raw materials in parts by mass:
tetraglycerol: 100 parts of (A);
saturated fatty acids: 30-60 parts;
stannous octoate: 1.5-2.5 parts;
acetic anhydride: 80-120 parts of a solvent;
epoxidized soybean oil: 20-30 parts of a solvent;
saponification rosin modified nano calcium carbonate: 3-8 parts.
2. The PVC environment-friendly plasticizer according to claim 1, characterized in that: the saturated fatty acid is C12～C18The saturated fatty acid of (4).
3. The PVC environment-friendly plasticizer according to claim 2, characterized in that: the saturated fatty acid is at least one of lauric acid, palmitic acid, myristic acid and stearic acid.
4. The PVC environment-friendly plasticizer according to any one of claims 1 to 3, characterized in that: the average particle size of the saponified rosin modified nano calcium carbonate is 40-90 nm.
5. The PVC environment-friendly plasticizer according to claim 4, wherein: the BET specific surface area of the saponified rosin modified nano calcium carbonate is 18-30 m2/g。
6. The PVC environment-friendly plasticizer according to claim 5, characterized in that: the saponified rosin modified nano calcium carbonate is obtained by activating and modifying nano calcium carbonate by using rosin saponification liquid with the mass fraction of 3.0-4.5%.
7. A preparation method of the PVC environment-friendly plasticizer according to any one of claims 1 to 6, characterized by comprising the following steps: the method comprises the following steps:
1) adding the tetraglycerol, the saturated fatty acid and the stannous octoate into a reaction kettle, and fully reacting at the temperature of 150-160 ℃ under the condition of 10-20 mbar;
2) cooling the materials in the reaction kettle to 100-110 ℃, adding acetic anhydride, and fully reacting under normal pressure;
3) and cooling the materials in the reaction kettle to normal temperature, adding epoxidized soybean oil and saponified rosin modified nano calcium carbonate, and emulsifying to obtain the PVC environment-friendly plasticizer.
8. The method of claim 7, wherein: the reaction time in the step 1) is 4-6 h.
9. The production method according to claim 7 or 8, characterized in that: the reaction time in the step 2) is 1-1.5 h.
10. The production method according to claim 7 or 8, characterized in that: the emulsifying time in the step 3) is 40-60 min.
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