CN111635510B - Environment-friendly caprolactone-based polyether ester plasticizer and synthesis method thereof - Google Patents
Environment-friendly caprolactone-based polyether ester plasticizer and synthesis method thereof Download PDFInfo
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- 239000004014 plasticizer Substances 0.000 title claims abstract description 39
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 30
- 229920000570 polyether Polymers 0.000 title claims abstract description 30
- 150000002148 esters Chemical class 0.000 title claims abstract description 25
- 238000001308 synthesis method Methods 0.000 title abstract description 4
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 25
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 11
- -1 ester polyol Chemical class 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- SSOZBCCITNPUMJ-UHFFFAOYSA-N 1-methoxycyclohexan-1-ol Chemical compound COC1(O)CCCCC1 SSOZBCCITNPUMJ-UHFFFAOYSA-N 0.000 claims description 5
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 claims description 5
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 5
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000007142 ring opening reaction Methods 0.000 claims description 5
- 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 description 5
- 229920005862 polyol Polymers 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000006640 acetylation reaction Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 238000007039 two-step reaction Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims 1
- 238000005886 esterification reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 229920000728 polyester Polymers 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 1
- 238000013508 migration Methods 0.000 abstract 1
- 230000005012 migration Effects 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 229920001610 polycaprolactone Polymers 0.000 description 11
- 239000004632 polycaprolactone Substances 0.000 description 11
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 4
- 238000006065 biodegradation reaction Methods 0.000 description 3
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 239000008037 PVC plasticizer Substances 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006084 composite stabilizer Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000003809 water extraction Methods 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to an environment-friendly caprolactone-based polyether ester plasticizer and a synthesis method thereof. Due to the ester bond in the structure of the plasticizer and the large molecular weight, the mobility of the plasticizer applied to polar high polymer materials such as PVC materials can be improved. The invention takes the degradable material caprolactone monomer as the basic raw material and does not contain o-benzene substances, so that the toxicity of the plasticizer is greatly reduced. The invention not only solves the problems of poor hardness, poor tensile strength and easy migration of the existing environment-friendly plasticizer, but also solves the problems of poor low-temperature flexibility, high bulk viscosity and low toughening efficiency of the polyester plasticizer.
Description
Technical Field
The invention belongs to the field of fine chemical synthesis and plastic additive application, and relates to an environment-friendly caprolactone-based polyether ester plasticizer and a synthesis method thereof.
Background
Plasticizers are among the largest plastic aids produced and consumed worldwide. China has become the country with the most plasticizer production and consumption in Asian regions. With the improvement of environmental protection consciousness of various countries in the world, the toxicity problem of the traditional collar benzene dicarboxylic acid PVC plasticizer is gradually paid attention to due to the collar benzene structure in the molecular chain. The plastic products such as medicine and food package, daily necessities, toys and the like have higher purity and sanitary requirements on the main plasticizer DOP and the like. Corresponding measures have been taken internationally to limit the scope of use of DOP. The swiss government has decided to ban the use of DOP in children's toys; in Germany, DOP is prohibited from being added into all plastic products related to human body hygiene and food; the addition of DOP is prohibited in medical device-related products in Japan. And the PVC product added with the traditional plasticizer has high degradation difficulty and can cause a great deal of pollution to the environment. At present, China has higher and higher requirements on environmental protection, and the field of plasticizers is also developed in the direction of easy degradation and low toxicity.
Caprolactone has been widely used in the field of degradable materials due to its good biocompatibility and degradability.
The polyether ester plasticizer contains ester group with strong polarity and ether group with weak polarity in its molecule, so that it possesses good high and low temperature resistance and good compatibility with polar high polymer, so that it is attracted by attention and has been used for plasticizing PVC material. The caprolactone-based polyether ester plasticizer has good biodegradability, so that the problem that the common polyether plasticizer is not biodegradable can be solved.
Disclosure of Invention
The invention aims to prepare an environment-friendly caprolactone-based polyether ester type biodegradable plasticizer through two-step reaction of ring opening and acetylation of caprolactone.
The invention utilizes the characteristic that the molecular weight of the caprolactone ring-opening polymerization is easy to control, realizes the regulation and control of the molecular weight of the product, and can regulate the length of the molecular chain segment of the caprolactone-based polyether ester plasticizer and the structure of the product according to the requirement of PVC products.
The invention introduces ether group and ester group during synthesis, so that the plasticizer can simultaneously have the basic properties of ether group and ester group without blending with other raw materials.
The technical scheme of the invention is as follows:
an environment-friendly caprolactone-based polyether ester plasticizer has a molecular structural formula as follows: r1(COC5H10O)nCOCH3In the molecular structural formula of R1The compound is any one of ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether and cyclohexanediol monomethyl ether, and n is 1-500, preferably 5-50 in the molecular structural formula.
A method for synthesizing an environment-friendly caprolactone-based polyether ester plasticizer comprises the following steps:
(1) ring-opening reaction of caprolactone: adding high-boiling-point ether alcohol and caprolactone monomers into a reactor, heating to 50-80 ℃, carrying out reduced pressure distillation for 1-4h, then testing moisture, and then adding a catalyst; wherein the molar ratio of the ether alcohol to the caprolactone is 1:0.5-3, the dosage of the catalyst is 0.0005-0.05 percent of the mass fraction of the reactant, the acid value and the residual amount of the reactant of a system are tested after the reaction is carried out for 3-10h by heating and stirring at the temperature of 120-160 ℃, and when the acid value and the residual amount of the reactant are qualified, the micromolecules are removed by reduced pressure distillation at the temperature of 120-160 ℃ for 2-4h, thus obtaining the polyalcohol with ether ester bonds.
(2) Acetylation reaction: adding acetic anhydride which is 5 to 11 percent of the molar excess of the polyether ester polyol into the polyether ester polyol, slowly dropwise adding the acetic anhydride, controlling the reaction temperature of the system to be 68 to 72 ℃, continuously stirring and reacting for 5 to 9 hours, and finishing the reaction when the temperature of the system is reduced to 30 ℃ to obtain the crude polyether ester.
(3) And (3) separation and purification of polyether ester: the crude polyether ester was distilled under reduced pressure to remove impurities and excess acetic anhydride, using 10% by weight NaHCO3And (3) neutralizing the solution, washing, separating water by using a separating funnel, and then performing reduced pressure dehydration to obtain a finished product of the polyether ester environment-friendly plasticizer.
The high-boiling-point ether alcohol is one of ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether and cyclohexanediol monomethyl ether.
The catalyst is one of stannous octoate, tetrabutyl titanate, zinc isooctoate and dibutyltin dilaurate.
The gain effect of the invention is as follows: compared with polyester obtained by conventional condensation, the polymer plasticizer obtained by ring opening of caprolactone has lower viscosity and chroma, and provides better compatibility and higher plasticizing efficiency for PVC base materials; and the plasticity of the base material can be improved, the strength of the base material can be kept more, and the base material can be more easily biodegraded.
Detailed Description
The following examples are further illustrative of the present invention, but the present invention is not limited thereto.
EXAMPLE 1 preparation of acetylated butoxydiethoxypolycaprolactone
Adding 162g of diethylene glycol monobutyl ether and 228g of caprolactone into a reaction kettle, distilling at 60 ℃ under reduced pressure until the water content is lower than 300ppm of the total reaction mass fraction, adding 0.039g of stannous octoate, heating to 150 ℃ to react until the caprolactone monomer content is lower than 1% of the total reaction mass, cooling to 140 ℃ to distill under reduced pressure for 2 hours, and stopping reaction to obtain polycaprolactone ether alcohol. Then adding 112g of acetic anhydride, controlling the adding speed of the acetic anhydride to ensure that the reaction temperature is controlled between 68 and 72 ℃ for reaction for 6 hours, and separating and purifying when the system is cooled to 30 ℃ to obtain the refined acetylated butoxy diethoxy polycaprolactone.
The acetylated butoxy diethoxy polycaprolactone is subjected to a biodegradation test according to a GB/T19277 detection method, and the decomposition rate in 20 days is 81.5%.
EXAMPLE 2 preparation of acetylated butoxytriethoxy polycaprolactone
Adding 206g of triethylene glycol monobutyl ether and 228g of caprolactone into a reaction kettle, distilling at 60 ℃ under reduced pressure until the water content is lower than the total reaction mass fraction of 300ppm, adding 0.035g of stannous octoate, heating to 150 ℃ to react until the caprolactone monomer content is lower than 1% of the total reaction mass, cooling to 140 ℃ to distill under reduced pressure for 2 hours, and stopping reaction to obtain polycaprolactone ether alcohol. Then adding 112g of acetic anhydride, controlling the adding speed of the acetic anhydride to control the reaction temperature to be between 68 and 72 ℃ for reaction for 6 hours, and separating and purifying when the system is cooled to 30 ℃ to obtain the refined acetylated butoxy triethoxy polycaprolactone.
Acetylated butoxytriethoxy polycaprolactone. Biodegradation is carried out according to the GB/T19277 detection method, and the 20-day decomposition rate is 80.3%.
EXAMPLE 3 preparation of acetylated Methoxycyclohexyloxy polycaprolactone
Adding 225g of cyclohexanediol monomethyl ether and 228g of caprolactone into a reaction kettle, distilling at 60 ℃ under reduced pressure until the water content is lower than 300ppm of the total reaction mass fraction, adding 0.035g of stannous octoate, heating to 150 ℃ to react until the caprolactone monomer content is lower than 1% of the total reaction mass, cooling to 140 ℃ to distill under reduced pressure for 2h, and stopping reaction to obtain polycaprolactone ether alcohol. Then adding 112g of acetic anhydride, controlling the adding speed of the acetic anhydride to control the reaction temperature to be between 68 and 72 ℃ for reaction for 6 hours, and separating and purifying when the system is cooled to 30 ℃ to obtain the refined acetylated methoxy cyclohexyloxy polycaprolactone.
The acetylated methoxy cyclohexyloxy polycaprolactone is subjected to biodegradation test according to a GB/T19277 detection method, and the decomposition rate in 20 days is 78.5%.
After mixing and grinding the polyether ester plasticizer prepared in example 1, example 2 and example 3 with 0.069g of barium stearate, 0.006g of bisphenol A, 0.015g of 1.3-diphenylpropane-1, 3-dione, 0.039g of magnesium aluminum hydroxycarbonate and 30g of OXYBVINYL 255F resin, plasticizer test was performed using ASTM D3291-97, ASTM D-1239-98, ASTM D-2240-; for comparison, the sheeting test was also conducted after replacing the polyether ester with diisononyl phthalate, and the following data were obtained.
TABLE 1 loss of plasticizer after tableting test results
The above results show that the polyether ester product of the present invention has water extraction resistance comparable to that of diisononyl phthalate, and has more outstanding oil extraction resistance than diisononyl phthalate
Examples 1, 2, 3 were tested as plasticizers in PVC sheets. 100 parts of PVC resin (SG-3) (comparison of three components of example 1 and example 2 and diisononyl phthalate) 50 parts, 5 parts of composite stabilizer GT301 and 5 parts of conductive carbon black T6601 and 5 parts are mixed according to the following mixing ratio; mixing by using a torque rheometer; after 24 hours at room temperature, the sample was prepared, and then a standard sample was prepared by using a standard sample mold. The results of the tests carried out according to GB/T1040-1992 are as follows.
TABLE 2 mechanical Property test results
| Plasticizer | Tensile Strength (MPa) | Elongation at Break (%) |
| Example 1 | 11.3 | 342 |
| Example 2 | 10.9 | 360 |
| Example 3 | 13.5 | 330 |
| Diisononyl phthalate | 11.1 | 260 |
The above results show that the invention has superior plasticising properties relative to diisononyl phthalate, tested for impact embrittlement temperature according to GB/T5470-1985. The test results were as follows:
TABLE 3 impact embrittlement temperature test results
| Plasticizer | Destruction rate (-30 ℃ C.) |
| Example 1 | 5/20 |
| Example 2 | 5/20 |
| Example 3 | 5/20 |
| Diisononyl phthalate | 7/20 |
The above results show that the present invention has more excellent low temperature flexibility than diisononyl phthalate.
The present invention is not limited to the above-mentioned embodiments, and any technical solutions similar or identical to the present invention, which are made in the light of the present invention, are within the scope of the present invention.
Claims (5)
1. An environment-friendly caprolactone-based polyether ester plasticizer has a molecular structural formula as follows: r1（COC5H10O）nCOCH3，
In the molecular structural formula of R1The compound is any one of ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether and cyclohexanediol monomethyl ether, and n =1-500 in the molecular structural formula, and is characterized in that:
taking caprolactone, micromolecular ether alcohol and acetic anhydride as raw materials, and obtaining the caprolactone-based polyether ester environment-friendly plasticizer through two-step reaction of ring opening and esterification of the caprolactone, wherein the specific reaction steps are as follows:
1) ring-opening reaction of caprolactone: adding high-boiling-point ether alcohol and caprolactone monomers into a reactor, heating to 50-80 ℃, carrying out reduced pressure distillation for 1-4h, then testing moisture, and then adding a catalyst; wherein the molar ratio of the ether alcohol to the caprolactone is 1:0.5-3, the dosage of the catalyst is 0.0005-0.05 percent of the mass fraction of the reactant, the acid value and the residual amount of the reactant of a system are tested after the reaction is carried out for 3-10h by heating and stirring at the temperature of 120-;
2) acetylation reaction: adding acetic anhydride which is 5 to 11 percent of the molar excess of the polyether ester polyol into the polyether ester polyol, slowly dropwise adding the acetic anhydride, controlling the reaction temperature of the system to be 68 to 72 ℃, continuously stirring and reacting for 5 to 9 hours, and finishing the reaction when the temperature of the system is reduced to 30 ℃ to obtain crude polyether ester;
3) and (3) separation and purification of polyether ester: the crude polyether ester was distilled under reduced pressure to remove impurities and excess acetic anhydride, using 10% by weight NaHCO3And neutralizing the solution, washing with water, separating out water, and performing reduced pressure dehydration to obtain the environment-friendly caprolactone-based polyether ester plasticizer finished product.
2. The environmentally friendly caprolactone-based polyetherester plasticizer according to claim 1, wherein n =5-50 in the structural formula.
3. An environmentally friendly caprolactone polyether ester plasticizer according to claim 1, wherein: the high-boiling-point ether alcohol is one of ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether and cyclohexanediol monomethyl ether.
4. An environmentally friendly caprolactone polyether ester plasticizer according to claim 1, wherein: the catalyst is one of stannous octoate, tetrabutyl titanate, zinc isooctoate and dibutyltin dilaurate.
5. The use of the environmentally friendly caprolactone-based polyetherester plasticizer according to claim 1, wherein: the plasticizer is applied to PVC resin and is used as a main plasticizer in PVC products.
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