CN112778510A - Degradable polyester rubber and preparation method and application thereof - Google Patents
Degradable polyester rubber and preparation method and application thereof Download PDFInfo
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- CN112778510A CN112778510A CN202011626549.3A CN202011626549A CN112778510A CN 112778510 A CN112778510 A CN 112778510A CN 202011626549 A CN202011626549 A CN 202011626549A CN 112778510 A CN112778510 A CN 112778510A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 121
- 239000005060 rubber Substances 0.000 title claims abstract description 120
- 229920000728 polyester Polymers 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000005886 esterification reaction Methods 0.000 claims abstract description 94
- 239000002253 acid Substances 0.000 claims abstract description 79
- 238000006243 chemical reaction Methods 0.000 claims abstract description 79
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000000539 dimer Substances 0.000 claims abstract description 74
- 230000032050 esterification Effects 0.000 claims abstract description 58
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 45
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 37
- 230000015556 catabolic process Effects 0.000 claims abstract description 36
- 238000006731 degradation reaction Methods 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 229920000151 polyglycol Polymers 0.000 claims abstract description 12
- 239000010695 polyglycol Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims description 54
- 238000010438 heat treatment Methods 0.000 claims description 17
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003921 oil Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 12
- VFGRALUHHHDIQI-UHFFFAOYSA-N butyl 2-hydroxyacetate Chemical compound CCCCOC(=O)CO VFGRALUHHHDIQI-UHFFFAOYSA-N 0.000 claims description 10
- 239000003607 modifier Substances 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims description 4
- -1 glycolic acid ester Chemical class 0.000 claims description 4
- 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 4
- 230000003373 anti-fouling effect Effects 0.000 claims description 3
- 229920000704 biodegradable plastic Polymers 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- NORCOOJYTVHQCR-UHFFFAOYSA-N propyl 2-hydroxyacetate Chemical compound CCCOC(=O)CO NORCOOJYTVHQCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000013535 sea water Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 55
- 229910052757 nitrogen Inorganic materials 0.000 description 27
- 238000012360 testing method Methods 0.000 description 24
- 238000004073 vulcanization Methods 0.000 description 17
- 229920003225 polyurethane elastomer Polymers 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- KRXBVZUTZPDWQI-UHFFFAOYSA-N ethane-1,2-diol;titanium Chemical compound [Ti].OCCO KRXBVZUTZPDWQI-UHFFFAOYSA-N 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 238000013329 compounding Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000004636 vulcanized rubber Substances 0.000 description 4
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910021485 fumed silica Inorganic materials 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003902 seawater pollution Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229920000954 Polyglycolide Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000004633 polyglycolic acid Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses degradable polyester rubber and a preparation method and application thereof. The preparation method comprises the following steps: under the vacuum condition, a first mixed reaction system containing dimer acid, polyglycols, an esterification catalyst and a polycondensation catalyst is subjected to primary esterification reaction; adding itaconic acid, ethylene glycol and a degradation regulator into the first mixed system to form a second mixed reaction system, and carrying out secondary esterification reaction at 130-150 ℃ for 2-4 h; and reducing the vacuum degree of the reaction system obtained after the secondary esterification reaction to be lower than 200Pa, and then carrying out polycondensation reaction at 200-230 ℃ for 4-6 h to obtain the degradable polyester rubber. The preparation method is short in process flow, the prepared degradable polyester rubber has good degradation performance and processability, and the rubber compound prepared from the polyester rubber shows excellent mechanical property and good degradation performance; meanwhile, the degradable polyester rubber prepared by the invention has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of rubber synthesis, and particularly relates to degradable polyester rubber as well as a preparation method and application thereof.
Background
Rubber materials have been gaining favor for their high elasticity and excellent heat resistance since their advent. The initial rubber is only one of natural rubber, and then, a variety of synthetic rubbers such as styrene butadiene rubber, isoprene rubber, nitrile butadiene rubber, chloroprene rubber and the like are gradually developed, but the rubbers have no degradability in the natural environment due to the characteristics of the main chain structure and chemical bonds, and the rubbers cause serious environmental pollution when being discarded in the natural environment. Dimer acid synthesized based on biochemical technology is a macromolecular dibasic acid with development prospect, and can be subjected to polycondensation with dihydric alcohol to obtain a polymer, but due to the fact that the hydrophobic property of the dimer acid and the hydrophilic property of most of micromolecular dihydric alcohol have large differences, the situation that reaction is incomplete when the dimer acid is introduced into a polycondensation system, and the molecular weight is difficult to be increased occurs.
In recent years, due to the popularization of automobiles, in the field of oil-resistant seal rings and the like, a series of polyurethane rubbers (classified into polyester type and polyether type) have been developed according to the requirements of oil resistance, heat resistance and air tightness, wherein the polyester type polyurethane rubber is used in rubber components of soluble bridge plugs due to the excellent oil resistance and the partially degradable characteristic. However, most of the polyester components of the rubber are polyethylene glycol adipate or polycaprolactone, and then the rubber is reacted with isocyanate groups to generate urethane bonds to connect the components (polyester polyol segments) to form raw polyurethane rubber. Although its polyester component has good degradation properties, the polyester urethanes are only partially degradable due to the presence of a large number of non-degradable urethane chemical bonds. Patent CN106030023A reports a degradable sealing ring for a bridge plug of an oil extraction tool after polyurethane rubber is modified to be made into a rubber compound. Although this method of adding a degradation agent to urethane rubber can achieve a certain effect, it is also likely to cause deterioration in mechanical properties of the material. In practical use, although the sealing ring made of polyurethane rubber compound can be partially degraded in high-temperature hot water, a large amount of large residues are generated after degradation, the residues can cause the blockage of pipelines such as oil gas pipelines, discharge holes and the like, and oil gas exploitation construction faults are caused, and the main reason is that the polyurethane rubber raw rubber is partially degradable. In the industry, there is also a common problem with polyurethane compounds, namely lower tear strength. Particularly, for rubber parts such as sealing parts for oil and gas exploitation which need to work in a harsh environment, if the material itself does not have high enough tearing strength after the surface of the rubber parts is scratched, the rubber parts are very easy to tear, and the sealing failure is caused. In addition, in the field of marine antifouling, a coating technology developed based on a degradable polyester polyurethane technology (i.e., adding polyurethane rubber to a marine antifouling coating) is also being highly regarded, but the polyurethane rubber has a defect of partial degradability, and can cause a certain degree of damage to the marine environment even after long-term use. Therefore, a rubber material with excellent mechanical properties and degradation performance and flexible and controllable degradation speed needs to be found.
Disclosure of Invention
The invention mainly aims to provide degradable polyester rubber and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of degradable polyester rubber, which comprises the following steps:
under the vacuum condition, a first mixed reaction system containing dimer acid, polyglycols, an esterification catalyst and a polycondensation catalyst is subjected to primary esterification reaction;
adding itaconic acid, ethylene glycol and a degradation regulator into the first mixed system to form a second mixed reaction system, and carrying out secondary esterification reaction at 130-150 ℃ for 2-4 h;
and reducing the vacuum degree of the reaction system obtained after the secondary esterification reaction to be lower than 200Pa, and then carrying out polycondensation reaction at 200-300 ℃ for 4-6 h to obtain the degradable polyester rubber.
Further, the preparation method comprises the following steps: and under the condition that the vacuum degree is 500-1000 Pa, reacting the first mixed reaction system containing dimer acid, polyglycols, an esterification catalyst and a polycondensation catalyst at 120-130 ℃ for 1-2 h, and then heating to 140-145 ℃ for further reaction for 1-2 h, thereby completing the primary esterification reaction.
The embodiment of the invention also provides the degradable polyester rubber prepared by the method.
The embodiment of the invention also provides degradable polyester rubber, which has a structure shown in the formula (I):
wherein s, t, n, m and p are all natural numbers which are not 0; r1A dimer acid with two carboxyl groups removed, and has a molecular formula of C34H66；R2Has any one of the following structures:
the embodiment of the invention also provides application of the degradable polyester rubber in the fields of preparing degradable rubber sealing elements of bridge plugs for oil and gas engineering, matrix resin degradation modifiers of coatings for preventing seawater pollution, degradable rubber modified base materials, toughening modifiers of biodegradable plastics or special degradable tires or rubber compounds.
The embodiment of the invention also provides a rubber compound which at least comprises the degradable polyester rubber.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention adopts dimer acid and itaconic acid which are derived from binary acids of biomass, and introduces glycollate comonomer which has the function of improving degradation performance, and the main chain of the prepared degradable rubber is of a full polyester structure and has the characteristics of environmental protection and degradability;
(2) in the invention, dimer acid monomer is introduced in the polymerization process, so that a large number of flexible branched chain structures are introduced into the main chain of the prepared degradable rubber, and the flexible branched chains are very easy to form physical kinks, so that the prepared degradable polyester rubber shows excellent tear strength after being made into rubber compound, and the problem of low tear strength of the conventional polyurethane rubber for bridge plugs is solved;
(3) according to the invention, glycolic acid ester is adopted as a degradation rate regulator and is introduced in a monomer mode, so that the problem that the degradation of common polyurethane rubber is dependent on the addition of an auxiliary agent is solved, and the prepared rubber has adjustable degradation rate and good performance uniformity;
(4) compared with polyester type polyurethane rubber, the degradable polyester rubber prepared by the invention has no introduction of urethane bond, no large-particle residue after hydrolysis, excellent easy hydrolysis performance before and after vulcanization, and residue after hydrolysis can pass through a 100-mesh screen;
(5) the invention adopts the combination of two-step esterification and polycondensation, solves the problems of low reaction activity of dimer acids with common dihydric alcohol and low molecular weight of copolymer, and the degradable polyester rubber prepared by the method has the characteristic of high molecular weight;
(6) the degradable polyester rubber prepared by the invention has excellent processing performance and vulcanization characteristic, and wide application range.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an IR spectrum of a degradable polyester rubber prepared in example 1 of the present invention.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to propose the technical solution of the present invention, which will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
One aspect of an embodiment of the present invention provides a method for preparing a degradable polyester rubber, including:
under the vacuum condition, a first mixed reaction system containing dimer acid, polyglycols, an esterification catalyst and a polycondensation catalyst is subjected to primary esterification reaction;
adding itaconic acid, ethylene glycol and a degradation regulator into the first mixed system to form a second mixed reaction system, and carrying out secondary esterification reaction at 130-150 ℃ for 2-4 h;
and reducing the vacuum degree of the reaction system obtained after the secondary esterification reaction to be lower than 200Pa, and then carrying out polycondensation reaction at 200-230 ℃ for 4-6 h to obtain the degradable polyester rubber.
In some more specific embodiments, the preparation method comprises: and under the condition that the vacuum degree is 500-1000 Pa, reacting the first mixed reaction system containing dimer acid, polyglycols, an esterification catalyst and a polycondensation catalyst at 120-130 ℃ for 1-2 h, and then heating to 140-145 ℃ for further reaction for 1-2 h, thereby completing the primary esterification reaction.
Further, the primary esterification reaction is carried out under the stirring condition, and the stirring speed is 5-100 rpm.
In some more specific embodiments, the preparation method comprises: adding itaconic acid, ethylene glycol and a degradation regulator into the first mixed system to form the second mixed reaction system, and then carrying out secondary esterification reaction in a protective atmosphere.
Further, the secondary esterification reaction is carried out under the stirring condition, and the stirring speed is 5-100 rpm.
In some more specific embodiments, the method for preparing the degradable polyester rubber comprises:
(1) primary esterification: adding dimer acid, polyglycols, an esterification catalyst and a polymerization catalyst into a reaction kettle together according to a certain proportion, starting stirring for 5-100 r/min, carrying out esterification reaction for 1-2 h under the conditions of high vacuum of 500-1000 Pa (absolute pressure) and reaction temperature of 120-130 ℃, then heating to 140-145 ℃, and continuing the reaction for 1-2 h to complete primary esterification;
(2) secondary esterification: continuously adding itaconic acid, ethylene glycol and a degradation regulator into the reaction kettle in proportion, and stirring for 5-100 r/min at the normal pressure of 130-150 ℃ under the protection of nitrogen to react for 2-4 h;
(3) polycondensation: starting stirring for 5-100 r/min, gradually increasing the vacuum degree until the absolute pressure of the reaction is lower than 200Pa, reacting for 4-6 h at the temperature of 200-230 ℃, and extruding by using nitrogen to obtain the degradable polyester rubber.
In some more specific embodiments, the dimer acid is a dimer of unsaturated fatty acids, a dibasic acid of formula C36H68O4。
Further, the polyglycols include any one of triethylene glycol, tetraethylene glycol, or a combination of both, and are not limited thereto.
Furthermore, the middle of the multi-glycol molecule is provided with ether bond, the flexibility of the main chain of the polymer obtained by taking the ether bond as a polymerization monomer through polycondensation is good, and the multi-glycol has the characteristic of high boiling point and can realize esterification under the conditions of high temperature and high vacuum.
Further, the esterification catalyst is any one or a combination of two or more of tetraethylammonium bromide, tetrapropylammonium bromide and tetrabutylammonium bromide, and is not limited thereto.
The esterification catalyst of the present invention is also a phase transfer catalyst with excellent performance, so that the conversion rate of the esterification reaction of acid and alcohol with poor compatibility can be improved.
Further, the polycondensation catalyst includes any one or a combination of two or more of tetrabutyl titanate, tetraisopropyl titanate, titanium glycol, and is not limited thereto.
Further, the molar ratio of the dimer acid to the polyglycols is 1: 1.5-1: 2.
Further, the molar ratio of the dimer acid to the esterification catalyst is 0.2: 100-1: 100.
In some more specific embodiments, the degradation modulator includes, without limitation, glycolate.
Further, the glycolic acid ester includes any one or a combination of two or more of methyl glycolate, ethyl glycolate, propyl glycolate, and butyl glycolate, but is not limited thereto.
In the invention, the introduction of glycolate as a comonomer can improve the degradation performance of the material, and compared with the method of directly adding polyglycolic acid for blending and introducing the glycolate in a comonomer mode, the material has more excellent uniformity and mechanical properties.
Further, the polycondensation reaction is carried out under the condition of stirring, and the stirring speed is 5-100 rpm.
Further, the molar ratio of the dimer acid to the itaconic acid is 1: 9-5: 5.
Further, the molar ratio of the itaconic acid to the ethylene glycol is 1: 1.1-1: 4.
Further, the molar ratio of the degradation regulator to the combination of the dimer acid and the itaconic acid is 1: 5-1: 20.
Further, the mass ratio of the polycondensation catalyst to the combination of the dimer acid and the itaconic acid (i.e., dibasic acid) is 0.02: 100-1: 100; wherein, the dimer acid and the itaconic acid both belong to dibasic acids.
Another aspect of an embodiment of the present invention also provides a degradable polyester rubber prepared by the foregoing method.
Another aspect of the embodiments of the present invention also provides a degradable polyester rubber having a structure represented by formula (I):
wherein s, t, n, m and p are all natural numbers which are not 0; r1A dimer acid with two carboxyl groups removed, and has a molecular formula of C34H66；R2Has any one of the following structures:
further, the ratio of s to t is 1: 9-5: 5, and the ratio of s to n is 1: 1.5-1: 2, and the ratio of (s + t) to p is 1: 5-1: 20.
Further, in the structure shown in the formula (I), the parenthesis in the structure shows the monomer units on the main chain of the polyester rubber synthesized by the preparation method of the invention, and each monomer unit is arranged without any exception, wherein: s corresponds to the number of dimer acid monomer units, t corresponds to the number of multi-glycol monomer units, n corresponds to the number of itaconic acid monomer units, m corresponds to the number of glycol monomer units, and p corresponds to the number of glycollate monomer units as a degradation accelerator. s, t, n, m, p are all natural numbers other than 0.
Further, R2Is a structure of tetraethylene glycol without two hydroxyl groups (molecular formula is C)8H16O3) Or a structure of triethylene glycol without two hydroxyl groups (molecular formula is C)6H12O2)
The invention also provides application of the degradable polyester rubber in the fields of preparing degradable rubber sealing elements of bridge plugs for oil and gas engineering, matrix resin degradation modifiers of coatings for preventing seawater pollution, degradable rubber modified base materials, toughening modifiers of biodegradable plastics or special degradable tires, rubber compounds or vulcanized rubber.
Another aspect of the embodiments of the present invention also provides a rubber compound, which at least includes the degradable polyester rubber.
In some more specific embodiments, the rubber compound comprises the following components in parts by mass: 60 parts of the degradable polyester rubber, 30 parts of fumed silica, 1 part of stearic acid, 0.5 part of triallyl cyanurate and 2.5 parts of dicumyl peroxide; the preparation method of the rubber compound comprises the following steps: and uniformly mixing the degradable polyester rubber, the fumed silica, 1 part of stearic acid, triallyl cyanurate and dicumyl peroxide in an open mill to prepare the rubber compound.
In another aspect of the embodiments of the present invention, there is also provided a vulcanized rubber obtained by vulcanizing the aforementioned rubber compound.
Further, the temperature of the vulcanization treatment is 170 ℃, and the time is 6 min.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were dimer acid available from AR grade, reagents ltd, kuntongjiang; the raw polyurethane rubber is sourced from Changzhou Yuanchuang rubber Co., Ltd, and is of YC-12 polyester type. The remaining reagents were commercially available.
The apparatus and methods used in the present invention are those commonly used in the art, except where specifically indicated. The molecular weight and the molecular weight distribution coefficient of the degradable rubber are measured by using a 1515-.
Evaluating the mechanical property of the degradable rubber: because the degradable rubber obtained by the preparation method is raw rubber, the mechanical property of the degradable rubber is difficult to evaluate, and the degradable rubber must be prepared into rubber compound firstly and then vulcanized and tabletted to test the mechanical property. The preparation method of the rubber compound comprises the following steps: the raw materials, 60 parts of crude rubber, 30 parts of fumed silica, 1 part of stearic acid, 0.5 part of triallyl cyanurate and 2.5 parts of dicumyl peroxide are weighed according to the mass parts and evenly mixed in an open mill to prepare the rubber compound. Vulcanizing at 170 deg.C for 6min to obtain sample wafer for mechanical property test, and testing mechanical property and degradation property. The tensile properties of the vulcanized rubber compound were tested by GB/T528-2009 standard, and the tear properties of the vulcanized rubber compound were tested by GB/T529-2008 standard (pant type). Therefore, unless otherwise specified, the terms "tensile strength", "elongation at break" and "tear strength" in the present invention are all mechanical properties of the rubber compound.
And (3) testing the degradation performance: putting 10g of raw rubber or rubber compound into a glass bottle filled with 100ml of water, covering a bottle cap, placing the bottle in an oven at 80 ℃, after 240 hours, sieving rubber residues with a 100-mesh sieve, taking components which do not pass through the sieve, drying and weighing (the weight is recorded as m), testing the degradation rate, and calculating the degradation rate according to the following formula:
example 1
(1) Primary esterification: adding 0.1mol of dimer acid, 0.2mol of triethylene glycol, 0.001mol of tetraethylammonium bromide (the dosage is 1% of the mol of the dimer acid), 1.734g of ethylene glycol titanium (the dosage is 1% of the total mass of the dimer acid and the itaconic acid) into a reaction kettle, starting stirring for 100r/min, carrying out esterification reaction for 1h under the conditions of high vacuum 1000Pa (absolute pressure) and reaction temperature of 120 ℃, then heating to 140 ℃, and continuing to react for 1h to complete primary esterification;
(2) secondary esterification: continuously adding 0.9mol of itaconic acid, 1.8mol of ethylene glycol and 0.05mol of methyl glycolate into the reaction kettle, and reacting for 4 hours at the temperature of 130 ℃ and normal pressure under the protection of nitrogen and at the stirring speed of 80 r/min;
(3) polycondensation: stirring for 100r/min, gradually increasing the vacuum degree to the absolute pressure of 200Pa, reacting at 200 deg.C for 6h, and extruding with nitrogen gas to obtain degradable polyester rubber (infrared spectrum is shown in figure 1).
Table 2 shows the results of the tests of the degradable polyester rubber of the present example after mixing and vulcanization.
Example 2
(1) Primary esterification: adding 0.2mol of dimer acid, 0.3mol of triethylene glycol, 0.001mol of tetrabutylammonium bromide (the amount is 0.5% of the mol amount of dimer acid), 1.084g of tetrabutyl titanate (the amount is 0.5% of the total mass of dimer acid and itaconic acid) into a reaction kettle, starting stirring at a speed of 5r/min, carrying out esterification reaction for 2 hours under the conditions of high vacuum 500Pa (absolute pressure) and reaction temperature of 130 ℃, then heating to 145 ℃, and continuing to react for 2 hours to complete primary esterification;
(2) secondary esterification: continuously adding 0.8mol of itaconic acid, 2.4mol of ethylene glycol and 0.1mol of ethyl glycolate into the reaction kettle, and reacting for 2 hours at the temperature of 150 ℃ and normal pressure under the protection of nitrogen and at the stirring speed of 5 r/min;
(3) polycondensation: starting stirring for 5r/min, gradually increasing the vacuum degree to 80Pa absolute pressure of reaction, reacting for 4h at 230 ℃, and extruding by nitrogen to obtain the degradable polyester rubber.
Table 2 shows the results of the tests of the degradable polyester rubber of the present example after mixing and vulcanization.
Example 3
(1) Primary esterification: adding 0.3mol of dimer acid, 0.54mol of triethylene glycol, 0.0006mol of tetrapropylammonium bromide (the dosage is 0.2% of the mol amount of dimer acid), and 0.052g of tetraisopropyl titanate (the dosage is 0.02% of the total mass of dimer acid and itaconic acid) into a reaction kettle, starting stirring for 100r/min, carrying out esterification reaction for 2h under the conditions of high vacuum 800Pa (absolute pressure) and reaction temperature of 130 ℃, then heating to 140 ℃, and continuing to react for 1h to complete primary esterification;
(2) secondary esterification: continuously adding 0.7mol of itaconic acid, 2.8mol of ethylene glycol and 0.6667mol of propyl glycolate into the reaction kettle, and reacting for 3 hours at the temperature of 140 ℃ and normal pressure under the protection of nitrogen and at the stirring speed of 50 r/min;
(3) polycondensation: starting stirring for 20r/min, gradually increasing the vacuum degree to the absolute pressure of 100Pa for reaction, reacting for 5h at 215 ℃, and extruding by using nitrogen to obtain the degradable polyester rubber.
Table 2 shows the results of the tests of the degradable polyester rubber of the present example after mixing and vulcanization.
Example 4
(1) Primary esterification: adding 0.4mol of dimer acid, 0.64mol of triethylene glycol, 0.0012mol of tetrapropylammonium bromide (the dosage is 0.3% of the mole of the dimer acid), and 0.1822g of ethylene glycol titanium (the dosage is 0.06% of the total mass of the dimer acid and the itaconic acid) into a reaction kettle, starting stirring for 50r/min, carrying out esterification reaction for 1.5h under the conditions of high vacuum 600Pa (absolute pressure) and reaction temperature of 130 ℃, then heating to 140 ℃, and continuing to react for 1h to complete primary esterification;
(2) secondary esterification: continuously adding 0.6mol of itaconic acid, 0.9mol of ethylene glycol and 0.1mol of butyl glycolate into the reaction kettle, and reacting for 4 hours at the temperature of 150 ℃ and normal pressure under the protection of nitrogen and at the stirring speed of 50 r/min;
(3) polycondensation: starting stirring for 40r/min, gradually increasing the vacuum degree to 50Pa absolute pressure of reaction, reacting for 4h at 220 ℃, and extruding by nitrogen to obtain the degradable polyester rubber.
Table 2 shows the results of the tests of the degradable polyester rubber of the present example after mixing and vulcanization.
Example 5
(1) Primary esterification: adding 0.5mol of dimer acid, 0.75mol of triethylene glycol, 0.001mol of tetrapropylammonium bromide (the dosage is 0.2% of the mol of dimer acid), and 0.2082g of ethylene glycol titanium (the dosage is 0.06% of the total mass of dimer acid and itaconic acid) into a reaction kettle, starting stirring for 20r/min, carrying out esterification reaction for 2h under the conditions of high vacuum 600Pa (absolute pressure) and reaction temperature of 130 ℃, then heating to 140 ℃, and continuing to react for 1h to complete primary esterification;
(2) secondary esterification: continuously adding 0.5mol of itaconic acid, 0.55mol of ethylene glycol and 0.2mol of methyl glycolate into the reaction kettle, and reacting for 3 hours at the temperature of 140 ℃ and normal pressure under the protection of nitrogen and at the stirring speed of 20 r/min;
(3) polycondensation: starting stirring for 20r/min, gradually increasing the vacuum degree to 80Pa absolute pressure of reaction, reacting for 5h at 205 ℃, and extruding by nitrogen to obtain the degradable polyester rubber.
Table 2 shows the results of the tests of the degradable polyester rubber of the present example after mixing and vulcanization.
Example 6 (comparison with example 4, otherwise, only triethylene glycol was replaced by 4 ethylene glycol)
(1) Primary esterification: adding 0.4mol of dimer acid, 0.64mol of tetraethylene glycol, 0.0012mol of tetrapropylammonium bromide (the dosage is 0.3% of the mol amount of the dimer acid), and 0.1822g of ethylene glycol titanium (the dosage is 0.06% of the total mass of the dimer acid and the itaconic acid) into a reaction kettle, starting stirring for 50r/min, carrying out esterification reaction for 1.5h under the conditions of high vacuum 600Pa (absolute pressure) and reaction temperature of 130 ℃, then heating to 140 ℃, and continuing to react for 1h to complete primary esterification;
(2) secondary esterification: continuously adding 0.6mol of itaconic acid, 0.9mol of ethylene glycol and 0.1mol of butyl glycolate into the reaction kettle, and reacting for 4 hours at the temperature of 150 ℃ and normal pressure under the protection of nitrogen and at the stirring speed of 50 r/min;
(3) polycondensation: starting stirring for 40r/min, gradually increasing the vacuum degree to 50Pa absolute pressure of reaction, reacting for 4h at 220 ℃, and extruding by nitrogen to obtain the degradable polyester rubber.
Table 2 shows the results of the tests of the degradable polyester rubber of the present example after mixing and vulcanization.
Example 7 (comparison with example 4, only the degree of vacuum of polycondensation was adjusted)
(1) Primary esterification: adding 0.4mol of dimer acid, 0.64mol of triethylene glycol, 0.0012mol of tetrapropylammonium bromide (the dosage is 0.3% of the mole of the dimer acid), and 0.1822g of ethylene glycol titanium (the dosage is 0.06% of the total mass of the dimer acid and the itaconic acid) into a reaction kettle, starting stirring for 50r/min, carrying out esterification reaction for 1.5h under the conditions of high vacuum 600Pa (absolute pressure) and reaction temperature of 130 ℃, then heating to 140 ℃, and continuing to react for 1h to complete primary esterification;
(2) secondary esterification: continuously adding 0.6mol of itaconic acid, 0.9mol of ethylene glycol and 0.1mol of butyl glycolate into the reaction kettle, and reacting for 4 hours at the temperature of 150 ℃ and normal pressure under the protection of nitrogen and at the stirring speed of 50 r/min;
(3) polycondensation: starting stirring for 40r/min, gradually increasing the vacuum degree to the absolute pressure of 250Pa for reaction, reacting for 4h at 220 ℃, and extruding by using nitrogen to obtain the degradable polyester rubber.
Table 2 shows the results of the tests of the degradable polyester rubber of the present example after mixing and vulcanization.
Example 8 (in comparison with example 4, the polycondensation temperature was adjusted and was not in the preferred range)
(1) Primary esterification: adding 0.4mol of dimer acid, 0.64mol of triethylene glycol, 0.0012mol of tetrapropylammonium bromide (the dosage is 0.3% of the mole of the dimer acid), and 0.1822g of ethylene glycol titanium (the dosage is 0.06% of the total mass of the dimer acid and the itaconic acid) into a reaction kettle, starting stirring for 50r/min, carrying out esterification reaction for 1.5h under the conditions of high vacuum 600Pa (absolute pressure) and reaction temperature of 130 ℃, then heating to 140 ℃, and continuing to react for 1h to complete primary esterification;
(2) secondary esterification: continuously adding 0.6mol of itaconic acid, 0.9mol of ethylene glycol and 0.1mol of butyl glycolate into the reaction kettle, and reacting for 4 hours at the temperature of 150 ℃ and normal pressure under the protection of nitrogen and at the stirring speed of 50 r/min;
(3) polycondensation: starting stirring for 40r/min, gradually increasing the vacuum degree to 50Pa absolute pressure of reaction, reacting for 4h at 190 ℃, and extruding by nitrogen to obtain the degradable polyester rubber.
Table 2 shows the results of the tests of the degradable polyester rubber of the present example after mixing and vulcanization.
Comparative example 1 (No esterification catalyst, compare with example 4)
(1) Primary esterification: adding 0.4mol of dimer acid, 0.64mol of triethylene glycol and 0.1822g of ethylene glycol titanium (the dosage is 0.06% of the total mass of the dimer acid and the itaconic acid) into a reaction kettle, starting stirring for 50r/min, carrying out esterification reaction for 1.5h under the conditions of high vacuum 600Pa (absolute pressure) and reaction temperature of 130 ℃, then heating to 140 ℃, and continuing the reaction for 1h to complete primary esterification;
(2) secondary esterification: continuously adding 0.6mol of itaconic acid, 0.9mol of ethylene glycol and 0.1mol of butyl glycolate into the reaction kettle, and reacting for 4 hours at the temperature of 150 ℃ and normal pressure under the protection of nitrogen and at the stirring speed of 50 r/min;
(3) polycondensation: stirring is started for 40r/min, the vacuum degree is gradually increased to 50Pa absolute pressure of reaction, and the reaction is carried out for 4h at the temperature of 220 ℃, so that the polymer is imploded and can not be extruded by nitrogen.
Table 2 shows the results of the tests on the polyester rubber of this comparative example and after compounding and vulcanization.
Comparative example 2 (without second stage esterification, with one stage esterification)
(1) Esterification: adding 0.4mol of dimer acid, 0.64mol of triethylene glycol, 0.0012mol of tetrapropylammonium bromide (the dosage is 0.3% of the mol amount of dimer acid), 0.1822g of ethylene glycol titanium (the dosage is 0.06% of the total mass of dimer acid and itaconic acid), 0.6mol of itaconic acid, 0.9mol of ethylene glycol and 0.1mol of butyl glycolate into a reaction kettle, starting stirring for 50r/min, carrying out esterification reaction for 1.5h under the conditions of high vacuum 600Pa (absolute pressure) and 130 ℃, then heating to 140 ℃, continuing to react for 1h, and finally reacting for 4h under the conditions of 150 ℃ normal pressure, nitrogen protection and stirring speed of 50 r/min;
(2) polycondensation: starting stirring for 40r/min, gradually increasing the vacuum degree to 50Pa absolute pressure of reaction, reacting for 4h at 220 ℃, and extruding by nitrogen to obtain the degradable polyester rubber.
Table 2 shows the results of the tests on the polyester rubber of this comparative example and after compounding and vulcanization.
Comparative example 3 (in comparison with example 4, the structure of the polyethylene glycol 400 is similar to that of triethylene glycol and tetraethylene glycol)
(1) Primary esterification: adding 0.4mol of dimer acid, 0.64mol of polyethylene glycol 400 (also counted as the polyethylene glycol), 0.0012mol of tetrapropylammonium bromide (the dosage is 0.3% of the mole amount of the dimer acid), and 0.1822g of ethylene glycol titanium (the dosage is 0.06% of the total mass of the dimer acid and the itaconic acid) into a reaction kettle, starting stirring for 50r/min, carrying out esterification reaction for 1.5h under the conditions of high vacuum 600Pa (absolute pressure) and the reaction temperature of 130 ℃, then heating to 140 ℃, and continuing to react for 1h to complete primary esterification;
(2) secondary esterification: continuously adding 0.6mol of itaconic acid, 0.9mol of ethylene glycol and 0.1mol of butyl glycolate into the reaction kettle, and reacting for 4 hours at the temperature of 150 ℃ and normal pressure under the protection of nitrogen and at the stirring speed of 50 r/min;
(3) polycondensation: starting stirring for 40r/min, gradually increasing the vacuum degree to 50Pa absolute pressure of reaction, reacting for 4h at 220 ℃, and extruding by nitrogen to obtain the degradable polyester rubber.
Table 2 shows the results of the tests on the polyester rubber of this comparative example and after compounding and vulcanization.
Comparative example 4 (without glycolate (degradation modifier), remainder example 4)
(1) Primary esterification: adding 0.4mol of dimer acid, 0.64mol of triethylene glycol, 0.0012mol of tetrapropylammonium bromide (the dosage is 0.3% of the mole of the dimer acid), and 0.1822g of ethylene glycol titanium (the dosage is 0.06% of the total mass of the dimer acid and the itaconic acid) into a reaction kettle, starting stirring for 50r/min, carrying out esterification reaction for 1.5h under the conditions of high vacuum 600Pa (absolute pressure) and reaction temperature of 130 ℃, then heating to 140 ℃, and continuing to react for 1h to complete primary esterification;
(2) secondary esterification: continuously adding 0.6mol of itaconic acid and 0.9mol of ethylene glycol into the reaction kettle, and reacting for 4 hours at the temperature of 150 ℃ and normal pressure under the protection of nitrogen and at the stirring speed of 50 r/min;
(3) polycondensation: starting stirring for 40r/min, gradually increasing the vacuum degree to 50Pa absolute pressure of reaction, reacting for 4h at 220 ℃, and extruding by nitrogen to obtain the degradable polyester rubber.
Table 2 shows the results of the tests on the polyester rubber of this comparative example and after compounding and vulcanization.
Comparative example 5 (overproof amount of dimer acid used)
(1) Primary esterification: adding 0.6mol of dimer acid, 0.96mol of triethylene glycol, 0.0018mol of tetrapropylammonium bromide (the dosage is 0.3% of the mole of the dimer acid), and 0.2342g of ethylene glycol titanium (the dosage is 0.06% of the total mass of the dimer acid and the itaconic acid) into a reaction kettle, starting stirring for 50r/min, carrying out esterification reaction for 1.5h under the conditions of high vacuum 600Pa (absolute pressure) and reaction temperature of 130 ℃, then heating to 140 ℃, and continuing to react for 1h to complete primary esterification;
(2) secondary esterification: continuously adding 0.4mol of itaconic acid, 0.6mol of ethylene glycol and 0.1mol of butyl glycolate into the reaction kettle, and reacting for 4 hours at the temperature of 150 ℃ and normal pressure under the protection of nitrogen and at the stirring speed of 50 r/min;
(3) polycondensation: starting stirring for 40r/min, gradually increasing the vacuum degree to 50Pa absolute pressure of reaction, reacting for 4h at 220 ℃, and extruding by nitrogen to obtain the degradable polyester rubber.
Table 2 shows the results of the tests on the polyester rubber of this comparative example and after compounding and vulcanization.
Comparative example 6
Replacing the degradable polyester rubber with commercially available polyurethane rubber raw rubber to perform a series of tests; table 2 shows the rubber of this comparative example and the test results after kneading and vulcanization.
TABLE 1 amounts of raw materials used in examples 1-8 and comparative examples 1-6
Note: "/" indicates no test or no data; (wherein dibasic acids refer to dimer acid and itaconic acid) Table 2 shows the results of rubber testing in examples 1-8 and comparative examples 1-6
Note: "/" indicates no test or no data
Compared with the conventional polyurethane rubber, the degradable polyester rubber has very remarkable advantages in mechanical properties, particularly tear strength, compared with the conventional polyurethane rubber, the polyester rubber obtained by the invention has very excellent degradability, the degradable polyester rubber synthesized by the preparation method of the invention and the rubber compound thereof show very good degradability under the condition of simulating the underground environment (hot water at 80 ℃ for 240 hours) of an oil and gas well, more than 85% of degraded particles can pass through a 100-mesh screen, the particles which are easily blocked by the oil and gas well and formed after underground degradation are very few, and the prepared degradable rubber sealing element can effectively reduce the construction risk when being used for oil and gas exploitation.
The degradation test performed in the present invention is actually a hydrolysis performance test, and the hydrolysis performance can be reflected by the degradation rate. "degradation" in the context of the present invention is understood to mean "hydrolysis".
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A preparation method of degradable polyester rubber is characterized by comprising the following steps:
under the vacuum condition, a first mixed reaction system containing dimer acid, polyglycols, an esterification catalyst and a polycondensation catalyst is subjected to primary esterification reaction;
adding itaconic acid, ethylene glycol and a degradation regulator into the first mixed system to form a second mixed reaction system, and carrying out secondary esterification reaction at 130-150 ℃ for 2-4 h;
and reducing the vacuum degree of the reaction system obtained after the secondary esterification reaction to be lower than 200Pa, and then carrying out polycondensation reaction at 200-230 ℃ for 4-6 h to obtain the degradable polyester rubber.
2. The production method according to claim 1, characterized by comprising:
under the condition that the vacuum degree is 500-1000 Pa, reacting a first mixed reaction system containing dimer acid, polyglycols, an esterification catalyst and a polycondensation catalyst at 120-130 ℃ for 1-2 h, and then heating to 140-145 ℃ for further reaction for 1-2 h, thereby completing the primary esterification reaction; preferably, the primary esterification reaction is carried out under the condition of stirring, and the stirring speed is 5-100 rpm.
3. The production method according to claim 1, characterized by comprising: adding itaconic acid, ethylene glycol and a degradation regulator into the first mixed system to form the second mixed reaction system, and then carrying out secondary esterification reaction in a protective atmosphere; preferably, the secondary esterification reaction is carried out under the condition of stirring, and the stirring speed is 5-100 rpm.
4. The method of claim 1, wherein: the dimer acid is a dimer of unsaturated fatty acids with a molecular formula of C36H68O4；
And/or, the polyglycols comprise triethylene glycol and/or tetraethylene glycol;
and/or, the esterification catalyst is one or the combination of more than two of tetraethyl ammonium bromide, tetrapropyl ammonium bromide and tetrabutyl ammonium bromide;
and/or the polycondensation catalyst comprises one or the combination of more than two of tetrabutyl titanate, tetraisopropyl titanate and titanium glycol;
and/or the molar ratio of the dimer acid to the polyglycols is 1: 1.5-1: 2;
and/or the molar ratio of the dimer acid to the esterification catalyst is 0.2: 100-1: 100.
5. The method of claim 1, wherein: the degradation modulator comprises a glycolic acid ester; preferably, the glycolic acid ester comprises any one or the combination of more than two of methyl glycolate, ethyl glycolate, propyl glycolate and butyl glycolate;
and/or the polycondensation reaction is carried out under the stirring condition, and the stirring speed is 5-100 rpm.
6. The method of claim 1, wherein: the molar ratio of the dimer acid to the itaconic acid is 1: 9-5: 5;
and/or the molar ratio of the itaconic acid to the ethylene glycol is 1: 1.1-1: 4;
and/or the molar ratio of the degradation modifier to the combination of dimer acid and itaconic acid is 1:5 to 1: 20;
and/or the mass ratio of the polycondensation catalyst to the combination of the dimer acid and the itaconic acid is 0.02: 100-1: 100.
7. A degradable polyester rubber prepared by the method of any one of claims 1 to 6.
8. A degradable polyester rubber is characterized in that: it has a structure as shown in formula (I):
wherein s, t, n, m and p are all natural numbers which are not 0; r1A dimer acid with two carboxyl groups removed, and has a molecular formula of C34H66；R2Has any one of the following structures:
preferably, the ratio of s to t is 1: 9-5: 5, and the ratio of s to n is 1: 1.5-1: 2, and the ratio of (s + t) to p is 1: 5-1: 20.
9. Use of the degradable polyester rubber of claim 7 or 8 in the field of preparing degradable rubber sealing parts of bridge plugs for oil and gas engineering, matrix resin degradation modifiers of coatings for seawater antifouling, degradable rubber modified base materials, toughening modifiers of biodegradable plastics or special degradable tires or rubber compounds.
10. A rubber composition comprising at least the degradable polyester rubber as claimed in claim 7 or 8.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116875036A (en) * | 2023-07-18 | 2023-10-13 | 达封(北京)科技有限公司 | Soluble polyurethane rubber and preparation method and application thereof |
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| CN114957634B (en) * | 2022-07-04 | 2023-12-22 | 华润化学材料科技股份有限公司 | Degradable polyester rubber and preparation method and application thereof |
| CN116875036A (en) * | 2023-07-18 | 2023-10-13 | 达封(北京)科技有限公司 | Soluble polyurethane rubber and preparation method and application thereof |
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Application publication date: 20210511 |