CN117209733A - Hydrophobic polyester elastomer and preparation method thereof - Google Patents
Hydrophobic polyester elastomer and preparation method thereof Download PDFInfo
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- CN117209733A CN117209733A CN202311373704.9A CN202311373704A CN117209733A CN 117209733 A CN117209733 A CN 117209733A CN 202311373704 A CN202311373704 A CN 202311373704A CN 117209733 A CN117209733 A CN 117209733A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 52
- 239000000806 elastomer Substances 0.000 title claims abstract description 52
- 229920000728 polyester Polymers 0.000 title claims abstract description 52
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 36
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 10
- 229920000570 polyether Polymers 0.000 claims abstract description 10
- 238000005886 esterification reaction Methods 0.000 claims abstract description 8
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 10
- YSRSBDQINUMTIF-UHFFFAOYSA-N decane-1,2-diol Chemical compound CCCCCCCCC(O)CO YSRSBDQINUMTIF-UHFFFAOYSA-N 0.000 claims description 8
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- XWAMHGPDZOVVND-UHFFFAOYSA-N 1,2-octadecanediol Chemical compound CCCCCCCCCCCCCCCCC(O)CO XWAMHGPDZOVVND-UHFFFAOYSA-N 0.000 claims description 3
- 229940031723 1,2-octanediol Drugs 0.000 claims description 3
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 3
- AEIJTFQOBWATKX-UHFFFAOYSA-N octane-1,2-diol Chemical compound CCCCCCC(O)CO AEIJTFQOBWATKX-UHFFFAOYSA-N 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 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 3
- BTOOAFQCTJZDRC-UHFFFAOYSA-N 1,2-hexadecanediol Chemical compound CCCCCCCCCCCCCCC(O)CO BTOOAFQCTJZDRC-UHFFFAOYSA-N 0.000 claims description 2
- DWANEFRJKWXRSG-UHFFFAOYSA-N 1,2-tetradecanediol Chemical compound CCCCCCCCCCCCC(O)CO DWANEFRJKWXRSG-UHFFFAOYSA-N 0.000 claims description 2
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 239000006085 branching agent Substances 0.000 claims description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 2
- 239000001639 calcium acetate Substances 0.000 claims description 2
- 235000011092 calcium acetate Nutrition 0.000 claims description 2
- 229960005147 calcium acetate Drugs 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 2
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 claims description 2
- ZITKDVFRMRXIJQ-UHFFFAOYSA-N dodecane-1,2-diol Chemical compound CCCCCCCCCCC(O)CO ZITKDVFRMRXIJQ-UHFFFAOYSA-N 0.000 claims description 2
- 229940119177 germanium dioxide Drugs 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 239000006224 matting agent Substances 0.000 claims description 2
- 239000006082 mold release agent Substances 0.000 claims description 2
- LJZULWUXNKDPCG-UHFFFAOYSA-N nonane-1,2-diol Chemical compound CCCCCCCC(O)CO LJZULWUXNKDPCG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 229960005196 titanium dioxide Drugs 0.000 claims description 2
- 235000010215 titanium dioxide Nutrition 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 229960000314 zinc acetate Drugs 0.000 claims description 2
- 235000013904 zinc acetate Nutrition 0.000 claims description 2
- 125000005474 octanoate group Chemical group 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- MCRZWYDXIGCFKO-UHFFFAOYSA-N 2-butylpropanedioic acid Chemical group CCCCC(C(O)=O)C(O)=O MCRZWYDXIGCFKO-UHFFFAOYSA-N 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 description 1
Abstract
The invention discloses a hydrophobic polyester elastomer and a preparation method thereof, and belongs to the technical field of polyester elastomers. The technical proposal is as follows: aromatic dibasic acid, branched dibasic acid, 1, 4-butanediol, long-chain branched dibasic alcohol and polyether glycol are taken as raw materials, and a catalyst and other auxiliary agents are added for esterification reaction and polycondensation reaction to obtain a polyester elastomer; wherein the addition amount of the branched chain dibasic acid is 5-20% of the total mass of the dibasic acid, the addition amount of the long chain dibasic alcohol is 5-30% of the total mass of the 1, 4-butanediol and the long chain dibasic alcohol, the ratio of the sum of the molar masses of the dibasic acid to the sum of the 1, 4-butanediol and the molar masses of the long chain dibasic alcohol is 1:1.2-2, and the mass ratio of the dibasic acid to the polyether dibasic alcohol is 0.25-4:1. According to the invention, the branched chain dibasic acid and the long-chain branched chain dihydric alcohol are introduced into the polyester elastomer, so that the hydrophobic property of the polyester elastomer can be greatly improved, the cooperativity is realized, and the mechanical property of the polyester elastomer is not influenced.
Description
Technical Field
The invention relates to the technical field of polyester elastomers, in particular to a hydrophobic polyester elastomer and a preparation method thereof.
Background
Thermoplastic polyester elastomer materials are widely applied to the fields of automobiles, electronic and electric appliances, industrial products, sports goods, films, medical treatment, blend alloys and the like due to the characteristics of high comprehensive mechanical properties, excellent heat resistance, outstanding chemical resistance, outstanding weather resistance and the like. In the use process of the polyester elastomer plastic product, the existence of water accelerates aging degradation, and in order to ensure the service life of the polyester elastomer plastic product, hydrophobic modification is often needed. The study and preparation of hydrophobic polyester elastomers is an important aspect of the functionalization modification of polyester elastomers.
The contact angle of hydrophobic plastics is generally greater than 90 °, and plastics are designed from molecular structures to improve their hydrophobic properties, typically by incorporating low surface energy materials into their molecules, as disclosed in patents CN114716653A, CN113501948A, US10100159B2, CN115926131a, to introduce long chain alkanes, fluoroalkyl groups, and silicones to increase the hydrophobicity of plastics. Although fluoroalkyl and silicone are more hydrophobic than long chain alkanes, they are costly and limited in application after plastic contains fluorine or silicon; whereas only conventional long chain alkanes are added, their hydrophobicity is generally. Thus, with the expansion of the application field of polyester elastomers, it is necessary to develop novel hydrophobic polyester elastomers.
Disclosure of Invention
The invention aims to solve the technical problems that: the hydrophobic polyester elastomer and the preparation method thereof overcome the defects of the prior art, and the hydrophobic property of the polyester elastomer can be greatly improved by introducing the branched chain dibasic acid and the long-chain branched chain dihydric alcohol into the polyester elastomer, so that the hydrophobic polyester elastomer has cooperativity and can not influence the mechanical property.
The technical scheme of the invention is as follows:
in the first aspect, the invention provides a preparation method of a hydrophobic polyester elastomer, which takes aromatic dibasic acid, branched dibasic acid, 1, 4-butanediol, long-branched dihydric alcohol and polyether dihydric alcohol as raw materials, and adds a catalyst and other auxiliary agents to carry out esterification reaction and polycondensation reaction to obtain the polyester elastomer; wherein the addition amount of the branched chain dibasic acid is 5-20% of the total mass of the dibasic acid, the addition amount of the long chain dibasic alcohol is 5-30% of the total mass of the 1, 4-butanediol and the long chain dibasic alcohol, the ratio of the sum of the molar masses of the dibasic acid to the sum of the 1, 4-butanediol and the molar masses of the long chain dibasic alcohol is 1:1.2-2, and the mass ratio of the dibasic acid to the polyether dibasic alcohol is 0.25-4:1.
Preferably, the aromatic diacid is one or more of terephthalic acid, phthalic acid, isophthalic acid, biphenyl dicarboxylic acid, and 2, 6-naphthalene dicarboxylic acid.
Preferably, the branched dibasic acid is one or two of the following two compounds:
；
。
preferably, the long chain branched diol is one or more of 1, 2-octanediol, 1, 2-nonanediol, 1, 2-decanediol, 1, 2-dihydroxydodecane, 1, 2-dihydroxytetradecane, 1, 2-dihydroxyhexadecane, and 1, 2-dihydroxyoctadecane.
Preferably, the polyether glycol is one or more of polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol.
Preferably, the polyether glycol has a number average molecular weight of 200 to 2000.
Preferably, the catalyst is one or more of zinc acetate, magnesium acetate, calcium acetate, titanium dioxide, germanium dioxide, antimony trioxide, antimony acetate, ethylene glycol antimony, polyethylene glycol antimony, triisobutyl aluminum, dibutyl tin oxide, stannous octoate, monobutyl triisooctoate, dioctyl tin oxide, tetrabutyl titanate and isopropyl titanate.
Preferably, the other auxiliary agent is one or more of an antioxidant, an anti-aging agent, a light stabilizer, a heat stabilizer, a branching agent, a mold release agent, a pigment, a lubricant and a matting agent.
Preferably, the temperature of the esterification reaction is 180-230 ℃ and the reaction time is 0.5-2h; the temperature of the polycondensation reaction is 240-280 ℃, the reaction time is 2-4h, and the vacuum degree is less than 100pa.
In a second aspect, the present invention also provides a hydrophobic polyester elastomer prepared by the above-described preparation method.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the branched chain dibasic acid and the long-chain branched chain dihydric alcohol are introduced into the polyester elastomer, so that the hydrophobic property of the polyester elastomer can be greatly improved, the cooperativity is realized, and the mechanical property of the polyester elastomer is not influenced.
Detailed Description
In order to enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be clearly and completely described below in connection with the embodiments of the present invention.
The various chemical reagents and chemicals mentioned in the present invention are all commonly known in the art unless specifically stated otherwise. The experimental methods in the examples of the present invention, for which specific conditions are not noted, were selected according to conventional methods and conditions, or according to the commodity specifications.
The test method in the embodiment of the invention comprises the following steps:
hardness: according to standard GB/T531.1-2008, the sample thickness is 4mm and the residence time is 3s.
Tensile strength: according to standard GB/T1040.2-2022, a test speed of 50mm/min was used.
Hydrophobicity detection: and adopting a static liquid drop method to measure the water contact angle of the surface of the material by using a contact angle goniometer at the ambient temperature, wherein the volume of the used water drop is 5 mu L, selecting 5 different positions of the sample for carrying out the test, and taking the average value of the contact angles of the 5 different positions as a test result.
Example 1
The preparation method of the hydrophobic polyester elastomer of the embodiment comprises the following steps: 0.9kg of terephthalic acid, 0.1kg of branched dibasic acid, 0.7kg of 1, 4-butanediol, 0.1kg of 1, 2-decanediol and polytetramethylene ether glycol (M) n =1000) 1kg, stannous octoate 2g, antioxidant 1010 g and antioxidant 168 g are added into a reaction kettle, and the temperature is raised to 180 ℃ under the protection of nitrogenAfter 1.5 hours of esterification, the polymerization temperature was raised to 240℃and polycondensation was carried out under a high vacuum of less than 100pa for 2.5 hours to obtain a polyester elastomer. Wherein the branched dibasic acid has the following structural formula:
。
example 2
The preparation method of the hydrophobic polyester elastomer of the embodiment comprises the following steps: 0.7kg of terephthalic acid, 0.1kg of 2, 6-naphthalene dicarboxylic acid, 0.2kg of branched chain dibasic acid, 0.6kg of 1, 4-butanediol, 0.04kg of 1, 2-decanediol, 1kg of polytetramethylene ether glycol (Mn=2000), 1.4g of ethylene glycol antimony, 1010 g of antioxidant and 168 g of antioxidant are added into a reaction kettle, the temperature is increased to 190 ℃ under the protection of nitrogen to carry out esterification reaction for 1h, and then the polymerization temperature is increased to 250 ℃ and polycondensation is carried out for 2h under a high vacuum of less than 100pa, thus obtaining the polyester elastomer. Wherein, the structural formula of the branched dibasic acid is as follows:
。
example 3
The preparation method of the hydrophobic polyester elastomer of the embodiment comprises the following steps: 0.9kg of terephthalic acid, 0.08kg of isophthalic acid, 0.06kg of branched dibasic acid, 0.6kg of 1, 4-butanediol, 0.2kg of 1, 2-octanediol, 0.1kg of polypropylene glycol (Mn=1000), 1.2kg of polytetramethylene ether glycol (Mn=1000), 0.8g of antimonous oxide, 1.2g of tetrabutyl titanate and 1098 g of antioxidant are added into a reaction kettle, the temperature is raised to 185 ℃ under the protection of nitrogen for esterification reaction for 1 hour, and then the polymerization temperature is raised to 250 ℃ and polycondensation is carried out for 2 hours under high vacuum of less than 100pa, thus obtaining the polyester elastomer. Wherein, the structural formula of the branched dibasic acid is as follows:
。
example 4
The difference from example 1 is that: the branched dibasic acid has the following structural formula:
。
example 5
The difference from example 1 is that: the amount of terephthalic acid added was 0.8kg, and the amount of branched dibasic acid added was 0.2kg.
Example 6
The difference from example 1 is that: 1, 2-decanediol was replaced with 1, 2-dihydroxyoctadecane.
Example 7
The difference from example 1 is that: the 1, 4-butanediol was added in an amount of 0.6kg and the 1, 2-decanediol was added in an amount of 0.2kg.
Comparative example 1
The difference from example 1 is that: the amount of terephthalic acid added was adjusted to 1kg without adding a branched dibasic acid.
Comparative example 2
The difference from example 1 is that: the amount of terephthalic acid added was 0.6kg, and the amount of branched dibasic acid added was 0.4kg.
Comparative example 3
The difference from example 1 is that: the branched diacid is replaced with butyl malonic acid.
Comparative example 4
The difference from example 1 is that: 1, 2-decanediol was not added, and the amount of 1, 4-butanediol added was adjusted to 0.8kg.
Comparative example 5
The difference from example 1 is that: the 1, 4-butanediol was added in an amount of 0.5kg and the 1, 2-decanediol was added in an amount of 0.3kg.
The polyester elastomers prepared in examples 1 to 7 and comparative examples 1 to 5 were subjected to tensile strength, elongation at break and contact angle tests, and the test results are shown in table 1:
TABLE 1
As can be seen from Table 1, the polyester elastomer prepared in the examples of the present invention has a water contact angle of 136 to 150 degrees, a Shore hardness of 44 to 50HD and a tensile strength of 22 to 34MPa.
As can be seen from the data of comparative examples 1-5 and comparative examples 1 and 3, the addition of specific branched diacid can greatly increase the hydrophobicity of the polyester elastomer, the water contact angle increases from 112 ° to 142 ° without branched diacid (comparative example 1), and the shore hardness and mechanical properties are almost free of loss; and after butyl malonic acid is adopted to replace the branched chain diacid, the water contact angle of the prepared polyester elastomer is only 123 degrees, and the water contact angle is greatly reduced. Meanwhile, as can be seen from comparative example 2, when the addition amount of the branched dibasic acid is too high, the prepared polyester elastomer has an increased water contact angle but a significantly reduced Shore hardness and tensile strength.
As can be seen from the data of comparative examples 1, 6-7 and 4, the addition of the long-chain branched diol can increase the hydrophobicity of the polyester elastomer and greatly increase the water contact angle; the hydrophobicity is increased along with the increase of the content of the long-chain branched diol and the methylene chain of the long-chain branched diol, the water contact angle can be increased to 145 degrees, and the Shore hardness and the mechanical strength are almost free from loss; likewise, as can be seen from comparative example 5, when the content of the long-chain branched diol exceeds 30%, although the hydrophobicity increases, the Shore hardness and tensile strength of the polyester elastomer are remarkably reduced, the Shore hardness of comparative example 5 is reduced to 35D, and the tensile strength is reduced to 18MPa.
In conclusion, the hydrophobic property of the polyester elastomer can be better improved by compounding the branched dibasic acid and the long-chain branched dibasic alcohol, and the Shore hardness and the mechanical strength of the polyester elastomer are hardly changed.
Claims (10)
1. The preparation method of the hydrophobic polyester elastomer is characterized in that aromatic dibasic acid, branched dibasic acid, 1, 4-butanediol, long-chain branched dibasic alcohol and polyether glycol are used as raw materials, and a catalyst and other auxiliary agents are added for esterification reaction and polycondensation reaction to obtain the polyester elastomer; wherein the addition amount of the branched chain dibasic acid is 5-20% of the total mass of the dibasic acid, the addition amount of the long chain dibasic alcohol is 5-30% of the total mass of the 1, 4-butanediol and the long chain dibasic alcohol, the ratio of the sum of the molar masses of the dibasic acid to the sum of the 1, 4-butanediol and the molar masses of the long chain dibasic alcohol is 1:1.2-2, and the mass ratio of the dibasic acid to the polyether dibasic alcohol is 0.25-4:1.
2. The method of preparing a hydrophobic polyester elastomer as claimed in claim 1, wherein the aromatic dibasic acid is one or more of terephthalic acid, phthalic acid, isophthalic acid, biphenyl dicarboxylic acid and 2, 6-naphthalene dicarboxylic acid.
3. The method of preparing a hydrophobic polyester elastomer as claimed in claim 1, wherein the branched dibasic acid is one or both of the following two compounds:
；
。
4. the method of preparing a hydrophobic polyester elastomer of claim 1, wherein the long chain branched diol is one or more of 1, 2-octanediol, 1, 2-nonanediol, 1, 2-decanediol, 1, 2-dihydroxydodecane, 1, 2-dihydroxytetradecane, 1, 2-dihydroxyhexadecane, and 1, 2-dihydroxyoctadecane.
5. The method of preparing a hydrophobic polyester elastomer as claimed in claim 1, wherein the polyether glycol is one or more of polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol.
6. The method of preparing a hydrophobic polyester elastomer as claimed in claim 1 or 5, wherein the polyether glycol has a number average molecular weight of 200 to 2000.
7. The method for preparing the hydrophobic polyester elastomer according to claim 1, wherein the catalyst is one or more of zinc acetate, magnesium acetate, calcium acetate, titanium dioxide, germanium dioxide, antimony trioxide, antimony acetate, ethylene glycol antimony, polyethylene glycol antimony, triisobutyl aluminum, dibutyl tin oxide, stannous octoate, tributyl triisostannous octoate, dioctyl tin oxide, tetrabutyl titanate and isopropyl titanate.
8. The method of preparing a hydrophobic polyester elastomer as claimed in claim 1, wherein the other auxiliary agent is one or more of an antioxidant, a light stabilizer, a heat stabilizer, a branching agent, a mold release agent, a pigment, a lubricant and a matting agent.
9. The method for preparing a hydrophobic polyester elastomer as claimed in claim 1, wherein the esterification reaction is carried out at a temperature of 180 to 230 ℃ for a reaction time of 0.5 to 2 hours; the temperature of the polycondensation reaction is 240-280 ℃, the reaction time is 2-4h, and the vacuum degree is less than 100pa.
10. A hydrophobic polyester elastomer prepared by the preparation method according to any one of claims 1 to 8.
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| CN202311373704.9A CN117209733A (en) | 2023-10-23 | 2023-10-23 | Hydrophobic polyester elastomer and preparation method thereof |
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