CN115746539A - PVC/TPU blending material system composition - Google Patents
PVC/TPU blending material system composition Download PDFInfo
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- CN115746539A CN115746539A CN202211484547.4A CN202211484547A CN115746539A CN 115746539 A CN115746539 A CN 115746539A CN 202211484547 A CN202211484547 A CN 202211484547A CN 115746539 A CN115746539 A CN 115746539A
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- 238000002156 mixing Methods 0.000 title claims abstract description 87
- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 32
- 239000003607 modifier Substances 0.000 claims abstract description 60
- 238000003756 stirring Methods 0.000 claims description 101
- 239000013067 intermediate product Substances 0.000 claims description 95
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 86
- 238000006243 chemical reaction Methods 0.000 claims description 85
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 54
- 238000001816 cooling Methods 0.000 claims description 37
- 238000001914 filtration Methods 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000011347 resin Substances 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 18
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 18
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000012074 organic phase Substances 0.000 claims description 18
- 238000002390 rotary evaporation Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001291 vacuum drying Methods 0.000 claims description 14
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012141 concentrate Substances 0.000 claims description 9
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 235000012424 soybean oil Nutrition 0.000 claims description 9
- 239000003549 soybean oil Substances 0.000 claims description 9
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 9
- 239000012760 heat stabilizer Substances 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 5
- 125000005442 diisocyanate group Chemical group 0.000 claims description 4
- 150000001261 hydroxy acids Chemical class 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- 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 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- SIIRPIVXUCXWEK-UHFFFAOYSA-N CC(OC=C(O)Cl)=O Chemical compound CC(OC=C(O)Cl)=O SIIRPIVXUCXWEK-UHFFFAOYSA-N 0.000 claims description 2
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 abstract description 43
- 125000003700 epoxy group Chemical group 0.000 abstract description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 11
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 239000004014 plasticizer Substances 0.000 abstract description 7
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 abstract description 6
- 125000004185 ester group Chemical group 0.000 abstract description 6
- 229920000728 polyester Polymers 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 229920001971 elastomer Polymers 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003431 cross linking reagent Substances 0.000 abstract description 3
- 239000000806 elastomer Substances 0.000 abstract description 3
- 230000036541 health Effects 0.000 abstract description 3
- 239000008029 phthalate plasticizer Substances 0.000 abstract description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 abstract description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 44
- 229920000915 polyvinyl chloride Polymers 0.000 description 43
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 38
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 28
- BLORRZQTHNGFTI-ZZMNMWMASA-L calcium-L-ascorbate Chemical compound [Ca+2].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] BLORRZQTHNGFTI-ZZMNMWMASA-L 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 15
- 230000008034 disappearance Effects 0.000 description 13
- 239000012948 isocyanate Substances 0.000 description 8
- 150000002513 isocyanates Chemical class 0.000 description 8
- 150000008064 anhydrides Chemical class 0.000 description 7
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 7
- SORBEIKZIPTJRS-UHFFFAOYSA-N 2-chloro-2-hydroxyacetic acid Chemical compound OC(Cl)C(O)=O SORBEIKZIPTJRS-UHFFFAOYSA-N 0.000 description 6
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 6
- 230000005012 migration Effects 0.000 description 6
- 238000013508 migration Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229940106681 chloroacetic acid Drugs 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- DLZPQJDDVWPHNU-UHFFFAOYSA-N C(C)(=O)OC=C.OC=CCl Chemical compound C(C)(=O)OC=C.OC=CCl DLZPQJDDVWPHNU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Resins (AREA)
Abstract
The invention relates to the technical field of high polymer materials, in particular to a PVC/TPU blending material system composition. When the phthalate plasticizer is added to promote the compatibility of the polyester TPU and PVC in the blending process, the phthalate micromolecule plasticizer is easy to migrate and separate out to the surface of the blending product, the service life of the blending product is shortened, and the potential threat to the human health is formed. Aiming at the problems, the invention provides a PVC/TPU blending material system composition, which is added with a self-made blending modifier, wherein the blending modifier takes vinyl chloride-vinyl acetate copolymer as a main chain, and a branched chain contains structures such as ester groups, epoxy groups, carbamate, fatty long carbon chains, hydroxyl groups, sulfydryl and the like, has good compatibility with TPU and PVC, has the functions of a compatilizer, a plasticizer and a stabilizer, and can be used as a cross-linking agent to hoop a TPU elastomer, thereby having the advantage of improving the dimensional stability of the material.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a PVC/TPU blending material system composition.
Background
Polyvinyl chloride (PVC) is a general plastic with low price, outstanding advantages and large yield, and is widely used in various industries of national economy. However, the soft PVC needs to add a large amount of low molecular weight plasticizer to reduce the hardness, so that the material has the defects of poor elasticity, easy plastic deformation, large loss of mechanical properties, poor durability and the like.
The polyester type Thermoplastic Polyurethane (TPU) has high elasticity of rubber and high hardness of plastics, and also has excellent wear resistance, low temperature resistance, chemical corrosion resistance and weather resistance, so that the mechanical property, elasticity and thermal stability of PVC can be effectively improved by blending the TPU and the PVC, and meanwhile, the flame retardance, corrosion resistance and other aspects of the TPU can also be improved.
Research shows that the solubility parameter of PVC is 9.5-10.8, the solubility parameter of TPU is about 10, and the possibility of blending compatibility exists between the two; however, when the difference in solubility parameters, Δ > 0.5, incompatibility is exhibited. During the blending processing of PVC/TPU (polyester), a small molecular weight phthalate plasticizer is usually added to promote the compatibility of the polyester TPU and PVC, however, the small molecular plasticizer is easy to migrate and separate out to the surface of the blending product, the service life of the blending product is shortened, and the blending product poses potential threats to human health.
Disclosure of Invention
The problems in the prior art are that: when the phthalate plasticizer is added to promote the compatibility of the polyester TPU and PVC in the blending process, the phthalate micromolecule plasticizer is easy to migrate and separate out to the surface of the blending product, the service life of the blending product is shortened, and the potential threat to the human health is formed.
Aiming at the problems, the invention provides a PVC/TPU blending material system composition which comprises the following components in parts by weight:
specifically, the blending modifier is prepared according to the following steps:
(1) Dissolving 1g of hydroxychlorovinyl acetate resin in 50mL of methyl isobutyl ketone and placing the solution in a constant pressure dropping funnel to obtain solution A;
(2) Dissolving 0.237-0.302g of diisocyanate and 0.1-1mg of catalyst A in 300mL of methyl isobutyl ketone, placing the mixture in a reactor, heating the temperature in the reactor to 60-90 ℃, starting dropwise adding the solution A under magnetic stirring, stirring a reaction system, keeping the temperature, reacting for 1-3 hours, standing, and cooling to room temperature to obtain a solution containing an intermediate product I;
(3) Adding 0.102-0.123g of hydroxy acid into the solution containing the intermediate product I, then heating the temperature of a reaction system to 40-80 ℃, stirring for reacting for 1-3h, standing after the reaction is finished, distilling under reduced pressure, concentrating, adding 400mL of ethyl acetate for dissolving, adding 300mL of deionized water into the solution system, stirring for 10min, standing for layering, taking an organic phase, drying with 55g of anhydrous sodium sulfate, filtering, performing rotary evaporation, and performing vacuum drying for 4h at 60 ℃ to obtain an intermediate product II;
(4) Dissolving 1.339-1.425g of intermediate product II in 50mL of N, placing N-dimethylformamide in a constant pressure dropping funnel to obtain a solution B;
(5) Placing 1.36g of epoxidized soybean oil, 0.02g of catalyst B and 40mL of N, N-dimethylformamide into a three-neck flask, heating to 100-130 ℃, dropwise adding the liquid B under stirring, stirring after dropwise adding, keeping the temperature for reaction for 1-3 hours, cooling the temperature of a reaction system to room temperature after reaction, distilling under reduced pressure, adding 50mL of isopropanol, stirring, filtering, collecting insoluble substances, and drying at 60 ℃ for 4 hours in vacuum to obtain an intermediate product III;
(6) Adding 1mol of phthalic anhydride and 1.2-1.5mol of mercaptoethanol into 300mL of dimethyl sulfoxide, heating to 155-180 ℃ under the protection of nitrogen, stirring for reaction for 2-5h, cooling, standing, vacuum concentrating, dissolving the concentrate into 300mL of ethyl acetate, adding 200mL of deionized water, stirring for 10min, standing for layering, taking an organic phase, drying with 50g of anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product IV;
(7) Dissolving 0.307g of the intermediate product IV in 40mL of N, placing N-dimethylformamide in a constant pressure dropping funnel to obtain a solution C;
(8) Placing 2.699-2.785g of intermediate product III, 0.05g of catalyst B and 50mL of N, N-dimethylformamide into a three-neck flask, beginning to dropwise add the solution C while stirring, stirring and reacting at 110-135 ℃ for 2-5h after dropwise addition is finished, then cooling the temperature of a reaction system to room temperature, concentrating, adding 50mL of methanol, stirring, filtering, collecting insoluble substances, and drying in vacuum at 60 ℃ for 4h to obtain the blending modifier.
Specifically, the diisocyanate includes toluene diisocyanate or isophorone diisocyanate.
Specifically, the hydroxy acid comprises glycolic acid or lactic acid.
Specifically, the catalyst A comprises at least one of dibutyltin dilaurate, stannous octoate, triethylenediamine or triethylamine.
Specifically, the catalyst B comprises at least one of triphenylphosphine, tetrabutylammonium bromide or N, N-dimethylbenzylamine.
Specifically, the heat stabilizer comprises at least one of an organic tin heat stabilizer, a calcium-zinc composite heat stabilizer and a phosphite heat stabilizer.
Advantageous effects
(1) The self-made blending modifier is added into the PVC/TPU blending material system composition, the blending modifier takes vinyl chloride-vinyl acetate copolymer as a main chain, and a branched chain contains structures such as ester group, epoxy group, carbamate, fat long carbon chain, hydroxyl group, sulfydryl group and the like, the main chain structure of the blending modifier is vinyl chloride-vinyl acetate copolymer, the vinyl chloride-vinyl acetate copolymer and PVC phase have highly similar structural units, and the blending modifier has excellent compatibility and dispersibility in the PVC resin according to 'similar intermiscibility';
(2) Ester groups, carbamate and epoxy groups in the self-made blending modifier have polarity, so that strong polarity acting force among PVC molecular chains can be relieved, and the self-made blending modifier has a plasticizing effect; in addition, the ester group and the epoxy group can capture HCl generated by PVC decomposition, and have excellent auxiliary stability effect;
(3) A large amount of fatty long carbon chains in the self-made blending modifier structure can provide a plasticizing effect, and the processing temperature of PVC is reduced;
(4) The sulfydryl in the self-made blending modifier structure can react with double bonds formed in the degradation process of PVC, so that the PVC is prevented from discoloring and deteriorating, and the blending modifier has excellent thermal stability; meanwhile, the chemical bond is linked to the PVC, so that the problem of migration and precipitation in the processing and using processes is further avoided;
(5) According to the self-made blending modifier, the macromolecular chains and PVC resin form chain entanglement among the molecular chains in the processing process, so that advanced plasticization is facilitated, and the low mobility of the blending modifier is effectively ensured;
(6) The self-made blending modifier contains an ester group, carbamate and a polyhydroxy structure, the structure of the self-made blending modifier is similar to that of TPU, the two structures have good compatibility, and the polyhydroxy structure in the blending modifier can form a hydrogen bond with the carbamate in the TPU, so that the compatibility is further improved;
(7) The self-prepared blending modifier is compatible with TPU and PVC, has the functions of a compatilizer, a plasticizer and a stabilizer, and can be used as a crosslinking agent to hoop TPU elastomer, so that the self-prepared blending modifier has the advantage of improving the dimensional stability of materials.
Detailed Description
The TPU used in the following examples and comparative examples of the invention is a Tahitawa WHT-1565IC polyurethane elastomer.
Example 1
A PVC/TPU blending material system composition comprises the following components in parts by weight:
the blending modifier is prepared according to the following steps:
(1) Dissolving 1g of hydroxychloroacetic resin in 50mL of methyl isobutyl ketone and placing the mixture in a constant pressure dropping funnel to obtain solution A, wherein the hydroxychloroacetic resin is hydroxy ternary chloroacetic resin LPOH;
(2) Dissolving 0.302g of isophorone diisocyanate and 0.1mg of dibutyltin dilaurate in 300mL of methyl isobutyl ketone, placing the mixture into a reactor, raising the temperature in the reactor to 70 ℃, starting dropwise adding the solution A under magnetic stirring, stirring a reaction system, keeping the temperature for reaction for 3 hours, standing, and cooling to room temperature to obtain a solution containing an intermediate product I, wherein the infrared data of the intermediate product 1 are as follows: 3328cm -1 : -a NH-narrow peak is present; 2275cm -1 : in the presence of isocyanate; 1768cm -1 : -C = O present; 744cm -1 : -C-Cl is present;
(3) Adding 0.123g of lactic acid into a solution containing an intermediate product I, then raising the temperature of a reaction system to 50 ℃, stirring for reaction for 3 hours, standing after the reaction is finished, distilling under reduced pressure, concentrating, adding 400mL of ethyl acetate for dissolving, adding 300mL of deionized water into the solution system, stirring for 10 minutes, standing for layering, taking an organic phase, drying with 55g of anhydrous sodium sulfate, filtering, performing rotary evaporation, and performing vacuum drying at 60 ℃ for 4 hours to obtain an intermediate product II, wherein the infrared data of the intermediate product II are as follows: 3392cm -1 、1751cm -1 : the presence of a carboxyl group; 3328cm -1 : -NH-narrow peaks are present and enhanced; 2275cm -1 : the isocyanic acid radical disappears; 1768cm -1 : ester-C = O present; 744cm -1 : -C-Cl is present;
(4) Dissolving 1.425g of intermediate product II in 50mL of N, N-dimethylformamide and placing the solution in a constant pressure dropping funnel to obtain solution B;
(5) Placing 1.36g of epoxidized soybean oil, 0.02g of N, N-dimethylbenzylamine and 40mL of N, N-dimethylformamide into a three-neck flask, heating to 110 ℃, dropwise adding the solution B under stirring, stirring after dropwise adding, keeping the temperature for reaction for 2 hours, cooling the temperature of a reaction system to room temperature after reaction, and distilling under reduced pressureAdding 50mL of isopropanol, stirring, filtering, collecting insoluble substances, and drying in vacuum at 60 ℃ for 4h to obtain an intermediate product III, wherein the infrared data of the intermediate product III are as follows: 3392cm -1 、1751cm -1 : disappearance of carboxyl; 3351cm -1 、1052cm -1 : secondary-OH is present; 3328cm -1 : -NH-narrow peaks are present; 1770cm -1 : ester-C = O present; 943cm -1 、824cm -1 : epoxy groups are present and weakened; 744cm -1 : -C-Cl is present;
(6) Adding 1mol of phthalic anhydride and 1.4mol of mercaptoethanol into 300mL of dimethyl sulfoxide, heating to 165 ℃ under the protection of nitrogen, stirring for reaction for 4 hours, cooling, standing, vacuum concentrating, dissolving the concentrate into 300mL of ethyl acetate, adding 200mL of deionized water, stirring for 10 minutes, standing for layering, taking an organic phase, drying with 50g of anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product IV, wherein the infrared data of the intermediate product IV is as follows: 1250cm -1 : the anhydride disappears; 3225cm -1 : -OH (carboxyl) is present; 1719cm -1 : -C = O present; 3024cm -1 : a benzene ring C-H exists; 2551cm -1 : -SH is present;
(7) Dissolving 0.307g of the intermediate product IV in 40mL of N, placing N-dimethylformamide in a constant pressure dropping funnel to obtain a solution C;
(8) Placing 2.785g of intermediate product III, 0.05g of N, N-dimethylbenzylamine and 50mL of N, N-dimethylformamide into a three-neck flask, dropwise adding the solution C while stirring, stirring at 110 ℃ for reaction for 3h after the dropwise adding is completed, then cooling the temperature of a reaction system to room temperature, concentrating, adding 50mL of methanol, stirring, filtering, collecting insoluble substances, and drying in vacuum at 60 ℃ for 4h to obtain a blending modifier (a =422, b =20 and C = 40), wherein the infrared data of the blending modifier are as follows: 3225cm -1 : -OH (carboxyl) disappearance; 3351cm -1 、1052cm -1 : secondary-OH is present; 3328cm -1 : -a NH-narrow peak is present; 1769cm -1 : ester-C = O present; 943cm -1 、824cm -1 : epoxy groups are present; 3024cm -1 : a benzene ring C-H exists; 2551cm -1 : -SH is present; 744cm -1 : -C-Cl.
Example 2 the same as example 1, except that the blending modifier was added in an amount of 2 parts by weight in example 2.
Example 3 the same as example 1 except that the blending modifier was added in an amount of 4 parts by weight in example 3.
Example 4 is the same as example 1 except that the blending modifier is added in an amount of 1 part by weight in example 4.
Example 5 the same as example 1 except that 5 parts by weight of the blending modifier was added in example 5.
Example 6
A PVC/TPU blending material system composition comprises the following components in parts by weight:
the blending modifier is prepared according to the following steps:
(1) Dissolving 1g of hydroxychloroacetic resin in 50mL of methyl isobutyl ketone and placing the solution in a constant pressure dropping funnel to obtain solution A, wherein the hydroxychloroacetic resin is hydroxy ternary chloroacetic resin LPOH;
(2) Dissolving 0.237g of toluene-2, 4-diisocyanate and 0.1mg of dibutyltin dilaurate in 300mL of methyl isobutyl ketone, placing the mixture into a reactor, raising the temperature in the reactor to 60 ℃, starting dropwise adding the solution A under magnetic stirring, then stirring the reaction system, keeping the temperature for reaction for 3 hours, standing, and cooling to room temperature to obtain a solution containing an intermediate product I, wherein the infrared data of the intermediate product I are as follows: 3328cm -1 : -a NH-narrow peak is present; 3058cm -1 : a benzene ring C-H exists; 2275cm -1 : the existence of isocyanic acid radical; 1768cm -1 : -C = O present; 744cm -1 : -C-Cl is present;
(3) 0.102g of glycolic acid was added to the solution containing intermediate I, after which the temperature of the reaction system was raisedAnd (2) stirring to react for 3 hours at 40 ℃, after the reaction is finished, standing, distilling under reduced pressure, concentrating, adding 400mL of ethyl acetate to dissolve, adding 300mL of deionized water into a solution system, stirring for 10min, standing for layering, taking an organic phase, drying with 55g of anhydrous sodium sulfate, filtering, performing rotary evaporation, and performing vacuum drying at 60 ℃ for 4 hours to obtain an intermediate product II, wherein the infrared data of the intermediate product II are as follows: 3392cm -1 、1751cm -1 : the presence of a carboxyl group; 3328cm -1 : -NH-narrow peaks are present and enhanced; 3058cm -1 : a benzene ring C-H exists; 2275cm -1 : isocyanate disappears; 1768cm -1 : ester-C = O present; 744cm -1 : -C-Cl is present;
(4) Dissolving 1.339g of intermediate product II in 50mL of N, N-dimethylformamide and placing the solution in a constant pressure dropping funnel to obtain solution B;
(5) Placing 1.36g of epoxidized soybean oil, 0.02g of N, N-dimethylbenzylamine and 40mL of N, N-dimethylformamide into a three-neck flask, heating to 100 ℃, dropwise adding the liquid B under stirring, stirring after dropwise adding is finished, keeping the temperature for reaction for 3 hours, cooling the temperature of a reaction system to room temperature after the reaction is finished, distilling under reduced pressure, adding 50mL of isopropanol, stirring, filtering, collecting insoluble substances, and drying in vacuum for 4 hours at 60 ℃ to obtain an intermediate product III, wherein the infrared data of the intermediate product III are as follows: 3392cm -1 、1751cm -1 : disappearance of carboxyl groups; 3351cm -1 、1052cm -1 : secondary-OH is present; 3328cm -1 : -NH-narrow peaks are present; 3058cm -1 : a benzene ring C-H exists; 1770cm -1 : ester-C = O present; 943cm -1 、824cm -1 : epoxy groups are present and weakened; 744cm -1 : -C-Cl is present;
(6) Adding 1mol of phthalic anhydride and 1.5mol of mercaptoethanol into 300mL of dimethyl sulfoxide, heating to 170 ℃ under the protection of nitrogen, stirring for reaction for 3h, cooling, standing, vacuum concentrating, dissolving the concentrate into 300mL of ethyl acetate, adding 200mL of deionized water, stirring for 10min, standing for layering, taking an organic phase, drying with 50g of anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product IV, wherein the infrared data of the intermediate product IV is as follows: 1250cm -1 : the anhydride disappears; 3225cm -1 : -OH (carboxyl) is present; 1719cm -1 : -C = O present; 3024cm -1 : a benzene ring C-H exists; 2551cm -1 : -SH is present;
(7) Dissolving 0.307g of the intermediate product IV in 40mL of N, placing N-dimethylformamide in a constant pressure dropping funnel to obtain a solution C;
(8) Placing 2.699g of intermediate product III, 0.05g of N, N-dimethylbenzylamine and 50mL of N, N-dimethylformamide into a three-neck flask, dropwise adding the solution C while stirring, stirring at 110 ℃ to react for 5 hours after the dropwise adding is finished, then cooling the temperature of a reaction system to room temperature, concentrating, adding 50mL of methanol, stirring, filtering, collecting insoluble substances, and drying in vacuum at 60 ℃ for 4 hours to obtain a blending modifier (a =422, b =20 and C = 40), wherein the infrared data of the blending modifier are as follows: 3225cm -1 : -OH (carboxyl) disappearance; 3351cm -1 、1052cm -1 : secondary-OH is present; 3328cm -1 : -a NH-narrow peak is present; 1769cm -1 : ester-C = O present; 943cm -1 、824cm -1 : epoxy groups are present; 3024cm -1 、3058cm -1 : a benzene ring C-H exists; 2551cm -1 : -SH is present; 744cm -1 : -C-Cl.
Example 7
A PVC/TPU blending material system composition comprises the following components in parts by weight:
the blending modifier is prepared according to the following steps:
(1) Dissolving 1g of hydroxychloroacetic resin in 50mL of methyl isobutyl ketone and placing the solution in a constant pressure dropping funnel to obtain solution A, wherein the hydroxychloroacetic resin is hydroxy ternary chloroacetic resin LPOH;
(2) Dissolving 0.302g of isophorone diisocyanate and 0.1mg of stannous octoate in 300mL of methyl isobutyl ketone, placing the mixture into a reactor, raising the temperature in the reactor to 70 ℃, dropwise adding the solution A under magnetic stirring, stirring a reaction system, keeping the temperature for reaction for 3 hours, standing, and cooling to room temperature to obtain a solution containing an intermediate product I, wherein the infrared data of the intermediate product I is：3328cm -1 : -a NH-narrow peak is present; 2275cm -1 : the existence of isocyanic acid radical; 1768cm -1 : -C = O present; 744cm -1 : -C-Cl is present;
(3) Adding 0.102g of glycolic acid into a solution containing an intermediate product I, then raising the temperature of a reaction system to 60 ℃, stirring for reaction for 2 hours, standing after the reaction is finished, distilling under reduced pressure, concentrating, adding 400mL of ethyl acetate for dissolving, adding 300mL of deionized water into the solution system, stirring for 10 minutes, standing for layering, taking an organic phase, drying with 55g of anhydrous sodium sulfate, filtering, performing rotary evaporation, and performing vacuum drying at 60 ℃ for 4 hours to obtain an intermediate product II, wherein the infrared data of the intermediate product II are as follows: 3392cm -1 、1751cm -1 : the presence of a carboxyl group; 3328cm -1 : -NH-narrow peaks are present and enhanced; 2275cm -1 : isocyanate disappears; 1768cm -1 : ester-C = O present; 744cm -1 : -C-Cl is present;
(4) Dissolving 1.404g of intermediate product II in 50mL of N, N-dimethylformamide and placing the solution in a constant pressure dropping funnel to obtain solution B;
(5) Placing 1.36g of epoxidized soybean oil, 0.02g of triphenylphosphine and 40mL of N, N-dimethylformamide into a three-neck flask, heating to 130 ℃, dropwise adding the B liquid under stirring, stirring and preserving heat for reaction for 1h after dropwise adding is completed, cooling the temperature of a reaction system to room temperature after the reaction is completed, carrying out reduced pressure distillation, adding 50mL of isopropanol, stirring, filtering, collecting insoluble substances, and carrying out vacuum drying at 60 ℃ for 4h to obtain an intermediate product III, wherein the infrared data of the intermediate product III are as follows: 3392cm -1 、1751cm -1 : disappearance of carboxyl; 3351cm -1 、1052cm -1 : secondary-OH is present; 3328cm -1 : -a NH-narrow peak is present; 1770cm -1 : ester-C = O present; 943cm -1 、824cm -1 : epoxy groups are present and weakened; 744cm -1 : -C-Cl is present;
(6) Adding 1mol phthalic anhydride and 1.5mol mercaptoethanol into 300mL dimethyl sulfoxide, heating to 155 ℃ under the protection of nitrogen, stirring for reaction for 5h, cooling, standing, vacuum concentrating, dissolving the concentrate into 300mL ethyl acetate, adding 200mL deionized water, stirring for 10min, standing for layering, taking the organic phase, and mixingDrying 50g of anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product IV, wherein the infrared data of the intermediate product IV are as follows: 1250cm -1 : the anhydride disappears; 3225cm -1 : -OH (carboxyl) is present; 1719cm -1 : -C = O present; 3024cm -1 : a benzene ring C-H exists; 2551cm -1 : -SH is present;
(7) Dissolving 0.307g of the intermediate product IV in 40mL of N, placing N-dimethylformamide in a constant pressure dropping funnel to obtain a solution C;
(8) Placing 2.764g of intermediate product III, 0.05g of triphenylphosphine and 50mL of N, N-dimethylformamide into a three-neck flask, beginning to stir and dropwise add the solution C while stirring, after the dropwise addition is completed, stirring and reacting at 135 ℃ for 2h, then cooling the temperature of a reaction system to room temperature, concentrating, adding 50mL of methanol, stirring, filtering, collecting insoluble substances, and drying in vacuum at 60 ℃ for 4h to obtain a blending modifier (a =422, b =20 and C = 40), wherein the infrared data of the blending modifier are as follows: 3225cm -1 : -OH (carboxyl) disappearance; 3351cm -1 、1052cm -1 : secondary-OH is present; 3328cm -1 : -a NH-narrow peak is present; 1769cm -1 : ester-C = O present; 943cm -1 、824cm -1 : the presence of an epoxy group; 3024cm -1 : a benzene ring C-H exists; 2551cm -1 : -SH is present; 744cm -1 : -C-Cl is present.
Example 8
A PVC/TPU blending material system composition comprises the following components in parts by weight:
the blending modifier is prepared according to the following steps:
(1) Dissolving 1g of hydroxychloroacetic acid resin in 50mL of methyl isobutyl ketone and placing the solution in a constant pressure dropping funnel to obtain solution A, wherein the hydroxychloroacetic acid resin is hydroxyl ternary chloroacetic acid resin UMOH;
(2) 0.237g of toluene-2, 6-diisocyanate and 0.5mg of triethylenediamine were dissolved in 300mL of methyl isobutyl ketone and placed in a reactor, the temperature in the reactor was raised to 90 ℃ and the mixture was magnetically stirredAnd (3) dropwise adding the solution A under stirring, then stirring the reaction system, keeping the temperature, reacting for 3 hours, standing, and cooling to room temperature to obtain a solution containing an intermediate product I, wherein the infrared data of the intermediate product I are as follows: 3328cm -1 : -a NH-narrow peak is present; 3058cm -1 : a benzene ring C-H exists; 2275cm -1 : in the presence of isocyanate; 1768cm -1 : -C = O present; 744cm -1 : -C-Cl is present;
(3) Adding 0.123g of lactic acid into a solution containing an intermediate product I, then raising the temperature of a reaction system to 80 ℃, stirring for reaction for 1h, standing after the reaction is finished, distilling under reduced pressure, concentrating, adding 400mL of ethyl acetate for dissolution, adding 300mL of deionized water into the solution system, stirring for 10min, standing for layering, taking an organic phase, drying with 55g of anhydrous sodium sulfate, filtering, performing rotary evaporation, and performing vacuum drying at 60 ℃ for 4h to obtain an intermediate product II, wherein the infrared data of the intermediate product II are as follows: 3392cm -1 、1751cm -1 : the presence of a carboxyl group; 3328cm -1 : -NH-narrow peaks are present and enhanced; 3058cm -1 : a benzene ring C-H exists; 2275cm -1 : isocyanate disappears; 1768cm -1 : ester-C = O present; 744cm -1 : -C-Cl is present;
(4) Dissolving 1.36g of intermediate product II in 50mL of N, N-dimethylformamide and placing the solution in a constant pressure dropping funnel to obtain solution B;
(5) Placing 1.36g of epoxidized soybean oil, 0.02g of tetrabutylammonium bromide and 40mL of N, N-dimethylformamide into a three-neck flask, heating to 120 ℃, dropwise adding the solution B under stirring, stirring after dropwise adding, keeping the temperature for reaction for 2 hours, cooling the temperature of a reaction system to room temperature after the reaction is finished, carrying out reduced pressure distillation, adding 50mL of isopropanol, stirring, filtering, collecting insoluble substances, and carrying out vacuum drying at 60 ℃ for 4 hours to obtain an intermediate product III, wherein the infrared data of the intermediate product III are as follows: 3392cm -1 、1751cm -1 : disappearance of carboxyl; 3351cm -1 、1052cm -1 : secondary-OH is present; 3328cm -1 : -a NH-narrow peak is present; 3058cm -1 : a benzene ring C-H exists; 1770cm -1 : ester-C = O present; 943cm -1 、824cm -1 : epoxy groups are present and weakened; 744cm -1 : -C-Cl is present;
(6) Adding 1mol of phthalic anhydride and 1.2mol of mercaptoethanol into 300mL of dimethyl sulfoxide, heating to 180 ℃ under the protection of nitrogen, stirring for reaction for 2h, cooling, standing, vacuum concentrating, dissolving the concentrate into 300mL of ethyl acetate, adding 200mL of deionized water, stirring for 10min, standing for layering, taking an organic phase, drying with 50g of anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product IV, wherein the infrared data of the intermediate product IV are as follows: 1250cm -1 : the anhydride disappears; 3225cm -1 : -OH (carboxyl) is present; 1719cm -1 : -C = O present; 3024cm -1 : a benzene ring C-H exists; 2551cm -1 : -SH is present;
(7) Dissolving 0.307g of the intermediate product IV in 40mL of N, placing N-dimethylformamide in a constant pressure dropping funnel to obtain a solution C;
(8) Placing 2.72g of intermediate product III, 0.05g of tetrabutylammonium bromide and 50mL of N, N-dimethylformamide into a three-neck flask, beginning to dropwise add the solution C while stirring, after the dropwise addition is completed, stirring and reacting at 130 ℃ for 2h, then cooling the temperature of a reaction system to room temperature, concentrating, adding 50mL of methanol, stirring, filtering, collecting insoluble substances, and drying in vacuum at 60 ℃ for 4h to obtain a blending modifier (a =465, b =24 and C = 45), wherein the infrared data of the blending modifier are as follows: 3225cm -1 : -OH (carboxyl) disappearance; 3351cm -1 、1052cm -1 : secondary-OH is present; 3328cm -1 : -a NH-narrow peak is present; 1769cm -1 : ester-C = O present; 943cm -1 、824cm -1 : epoxy groups are present; 3024cm -1 、3058cm -1 : a benzene ring C-H exists; 2551cm -1 : -SH is present; 744cm -1 : -C-Cl.
Example 9
A PVC/TPU blending material system composition comprises the following components in parts by weight:
the blending modifier is prepared according to the following steps:
(1) Dissolving 1g of hydroxychloroacetic acid resin in 50mL of methyl isobutyl ketone and placing the solution in a constant pressure dropping funnel to obtain solution A, wherein the hydroxychloroacetic acid resin is hydroxyl ternary chloroacetic acid resin UMOH;
(2) Dissolving 0.237g of toluene-2, 4-diisocyanate and 0.5mg of triethylamine in 300mL of methyl isobutyl ketone, placing the mixture in a reactor, raising the temperature in the reactor to 90 ℃, starting dropwise adding the solution A under magnetic stirring, stirring a reaction system, carrying out heat preservation reaction for 3 hours, standing, and cooling to room temperature to obtain a solution containing an intermediate product I, wherein the infrared data of the intermediate product I are as follows: 3328cm -1 : -a NH-narrow peak is present; 3058cm -1 : a benzene ring C-H exists; 2275cm -1 : the existence of isocyanic acid radical; 1768cm -1 : -C = O present; 744cm -1 : -C-Cl is present;
(3) Adding 0.102g of glycolic acid into a solution containing an intermediate product I, then raising the temperature of a reaction system to 80 ℃, stirring for reaction for 1h, standing after the reaction is finished, distilling under reduced pressure, concentrating, adding 400mL of ethyl acetate for dissolving, adding 300mL of deionized water into the solution system, stirring for 10min, standing for layering, taking an organic phase, drying with 55g of anhydrous sodium sulfate, filtering, performing rotary evaporation, and performing vacuum drying at 60 ℃ for 4h to obtain an intermediate product II, wherein the infrared data of the intermediate product II are as follows: 3392cm -1 、1751cm -1 : the presence of a carboxyl group; 3328cm -1 : -NH-narrow peaks are present and enhanced; 3058cm -1 : a benzene ring C-H exists; 2275cm -1 : isocyanate disappears; 1768cm -1 : ester-C = O present; 744cm -1 : -C-Cl is present;
(4) Dissolving 1.339g of intermediate product II in 50mL of N, N-dimethylformamide and placing the solution in a constant pressure dropping funnel to obtain solution B;
(5) Placing 1.36g of epoxidized soybean oil, 0.02g of triphenylphosphine and 40mL of N, N-dimethylformamide into a three-neck flask, heating to 130 ℃, dropwise adding the B liquid under stirring, stirring and preserving heat for reaction for 1h after dropwise adding is completed, cooling the temperature of a reaction system to room temperature after the reaction is completed, carrying out reduced pressure distillation, adding 50mL of isopropanol, stirring, filtering, collecting insoluble substances, and carrying out vacuum drying for 4h at 60 ℃ to obtain an intermediate product III, wherein the infrared data of the intermediate product III are as follows: 3392cm -1 、1751cm -1 : carboxy radicalThe base disappears; 3351cm -1 、1052cm -1 : secondary-OH is present; 3328cm -1 : -NH-narrow peaks are present; 3058cm -1 : a benzene ring C-H exists; 1770cm -1 : ester-C = O present; 943cm -1 、824cm -1 : epoxy groups are present and weakened; 744cm -1 : -C-Cl is present;
(6) Adding 1mol of phthalic anhydride and 1.2mol of mercaptoethanol into 300mL of dimethyl sulfoxide, heating to 180 ℃ under the protection of nitrogen, stirring for reaction for 2h, cooling, standing, vacuum concentrating, dissolving the concentrate into 300mL of ethyl acetate, adding 200mL of deionized water, stirring for 10min, standing for layering, taking an organic phase, drying with 50g of anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product IV, wherein the infrared data of the intermediate product IV is as follows: 1250cm -1 : the anhydride disappears; 3225cm -1 : -OH (carboxyl) is present; 1719cm -1 : -C = O present; 3024cm -1 : a benzene ring C-H exists; 2551cm -1 : -SH is present;
(7) Dissolving 0.307g of the intermediate product IV in 40mL of N, placing N-dimethylformamide in a constant pressure dropping funnel to obtain a solution C;
(8) Placing 2.699g of intermediate product III, 0.05g of triphenylphosphine and 50mL of N, N-dimethylformamide into a three-neck flask, beginning to dropwise add the solution C while stirring, after dropwise adding is completed, stirring and reacting at 135 ℃ for 2h, then cooling the temperature of a reaction system to room temperature, concentrating, adding 50mL of methanol, stirring, filtering, collecting insoluble substances, and drying in vacuum at 60 ℃ for 4h to obtain a blending modifier (a =465, b =24 and C = 45), wherein the infrared data of the blending modifier are as follows: 3225cm -1 : -OH (carboxyl) disappearance; 3351cm -1 、1052cm -1 : secondary-OH is present; 3328cm -1 : -a NH-narrow peak is present; 1769cm -1 : ester-C = O present; 943cm -1 、824cm -1 : the presence of an epoxy group; 3024cm -1 、3058cm -1 : a benzene ring C-H exists; 2551cm -1 : -SH is present; 744cm -1 : -C-Cl is present.
Example 10
A PVC/TPU blending material system composition comprises the following components in parts by weight:
the blending modifier is prepared according to the following steps:
(1) Dissolving 1g of hydroxychloroacetic resin in 50mL of methyl isobutyl ketone and placing the mixture in a constant pressure dropping funnel to obtain solution A, wherein the hydroxychloroacetic resin is hydroxyl ternary chloroacetic resin UMOH;
(2) Dissolving 0.237g of toluene-2, 6-diisocyanate and 0.5mg of stannous octoate in 300mL of methyl isobutyl ketone, placing the mixture in a reactor, raising the temperature in the reactor to 90 ℃, starting dropwise adding the solution A under magnetic stirring, then stirring a reaction system, keeping the temperature, reacting for 3 hours, standing, and cooling to room temperature to obtain a solution containing an intermediate product I, wherein the infrared data are as follows: 3328cm -1 : -NH-narrow peaks are present; 3058cm -1 : a benzene ring C-H exists; 2275cm -1 : the existence of isocyanic acid radical; 1768cm -1 : -C = O present; 744cm -1 : -C-Cl is present;
(3) Adding 0.102g of glycolic acid into a solution containing an intermediate product I, then raising the temperature of a reaction system to 60 ℃, stirring for reaction for 3 hours, standing after the reaction is finished, distilling under reduced pressure, concentrating, adding 400mL of ethyl acetate for dissolving, adding 300mL of deionized water into the solution system, stirring for 10 minutes, standing for layering, taking an organic phase, drying with 55g of anhydrous sodium sulfate, filtering, performing rotary evaporation, and performing vacuum drying at 60 ℃ for 4 hours to obtain an intermediate product II, wherein the infrared data are as follows: 3392cm -1 、1751cm -1 : the presence of a carboxyl group; 3328cm -1 : -NH-narrow peaks are present and enhanced; 3058cm -1 : a benzene ring C-H exists; 2275cm -1 : isocyanate disappears; 1768cm -1 : ester-C = O present; 744cm -1 : -C-Cl is present;
(4) Dissolving 1.229g of intermediate product II in 50mL of N, N-dimethylformamide and placing the solution in an isobaric dropping funnel to obtain solution B;
(5) Placing 1.36g epoxidized soybean oil, 0.02g N, N-dimethylbenzylamine and 40mL N, N-dimethylformamide into a three-neck flask, heating to 100 ℃, dropwise adding the solution B under stirring, and stirring after dropwise addingStirring and preserving heat for reaction for 3 hours, cooling the temperature of a reaction system to room temperature after the reaction is finished, distilling under reduced pressure, adding 50mL of isopropanol, stirring, filtering, collecting insoluble substances, and drying in vacuum for 4 hours at 60 ℃ to obtain an intermediate product III, wherein infrared data are as follows: 3392cm -1 、1751cm -1 : disappearance of carboxyl groups; 3351cm -1 、1052cm -1 : secondary-OH is present; 3328cm -1 : -NH-narrow peaks are present; 3058cm -1 : a benzene ring C-H exists; 1770cm -1 : ester-C = O present; 943cm -1 、824cm -1 : epoxy groups are present and weakened; 744cm -1 : -C-Cl is present;
(6) Adding 1mol of phthalic anhydride and 1.3mol of mercaptoethanol into 300mL of dimethyl sulfoxide, heating to 175 ℃ under the protection of nitrogen, stirring for reaction for 2 hours, cooling, standing, vacuum concentrating, dissolving the concentrate into 300mL of ethyl acetate, adding 200mL of deionized water, stirring for 10 minutes, standing for layering, taking an organic phase, drying with 50g of anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product IV, wherein the infrared data are as follows: 1250cm -1 : the anhydride disappears; 3225cm -1 : -OH (carboxyl) is present; 1719cm -1 : -C = O present; 3024cm -1 : a benzene ring C-H exists; 2551cm -1 : -SH is present;
(7) Dissolving 0.307g of the intermediate product IV in 40mL of N, placing N-dimethylformamide in a constant pressure dropping funnel to obtain a solution C;
(8) Placing 2.699g of intermediate product III, 0.05g of N, N-dimethylbenzylamine and 50mL of N, N-dimethylformamide into a three-neck flask, dropwise adding the solution C while stirring, stirring at 110 ℃ for reaction for 5 hours after the dropwise adding is completed, then cooling the temperature of a reaction system to room temperature, concentrating, adding 50mL of methanol, stirring, filtering, collecting insoluble substances, and drying in vacuum at 60 ℃ for 4 hours to obtain a blending modifier (a =465, b =24, C = 45), wherein the infrared data are as follows: 3225cm -1 : -OH (carboxyl) disappearance; 3351cm -1 、1052cm -1 : secondary-OH is present; 3328cm -1 : -a NH-narrow peak is present; 1769cm -1 : ester-C = O present; 943cm -1 、824cm -1 : the presence of an epoxy group; 3024cm -1 、3058cm -1 : a benzene ring C-H exists; 2551cm -1 : -SH is present; 744cm -1 : -C-Cl is present.
Example 11
A PVC/TPU blending material system composition comprises the following components in parts by weight:
the blending modifier is prepared according to the following steps:
(1) Dissolving 1g of hydroxychloroacetic acid resin in 50mL of methyl isobutyl ketone and placing the solution in a constant pressure dropping funnel to obtain solution A, wherein the hydroxychloroacetic acid resin is hydroxyl ternary chloroacetic acid resin UMOH;
(2) Dissolving 0.302g of isophorone diisocyanate and 0.5mg of dibutyltin dilaurate in 300mL of methyl isobutyl ketone, placing the mixture into a reactor, raising the temperature in the reactor to 70 ℃, dropwise adding the solution A under magnetic stirring, stirring a reaction system, keeping the temperature for reaction for 3 hours, standing, and cooling to room temperature to obtain a solution containing an intermediate product I, wherein the infrared data of the intermediate product I are as follows: 3328cm -1 : -a NH-narrow peak is present; 2275cm -1 : in the presence of isocyanate; 1768cm -1 : -C = O present; 744cm -1 : -C-Cl is present;
(3) Adding 0.123g of lactic acid into a solution containing an intermediate product I, then raising the temperature of a reaction system to 60 ℃, stirring for reaction for 2 hours, standing after the reaction is finished, distilling under reduced pressure, concentrating, adding 400mL of ethyl acetate for dissolving, adding 300mL of deionized water into the solution system, stirring for 10 minutes, standing for layering, taking an organic phase, drying with 55g of anhydrous sodium sulfate, filtering, performing rotary evaporation, and performing vacuum drying at 60 ℃ for 4 hours to obtain an intermediate product II, wherein the infrared data of the intermediate product II are as follows: 3392cm -1 、1751cm -1 : the presence of a carboxyl group; 3328cm -1 : -NH-narrow peaks are present and enhanced; 2275cm -1 : the isocyanic acid radical disappears; 1768cm -1 : ester-C = O present; 744cm -1 : -C-Cl is present;
(4) Dissolving 1.425g of intermediate product II in 50mL of N, N-dimethylformamide and placing the solution in a constant pressure dropping funnel to obtain a solution B;
(5) Placing 1.36g of epoxidized soybean oil, 0.02g of N, N-dimethylbenzylamine and 40mL of N, N-dimethylformamide into a three-neck flask, heating to 110 ℃, dropwise adding the liquid B under stirring, stirring after dropwise adding, keeping the temperature for reaction for 1h, cooling the temperature of a reaction system to room temperature after reaction, carrying out reduced pressure distillation, adding 50mL of isopropanol, stirring, filtering, collecting insoluble substances, and carrying out vacuum drying at 60 ℃ for 4h to obtain an intermediate product III, wherein the infrared data of the intermediate product III are as follows: 3392cm -1 、1751cm -1 : disappearance of carboxyl; 3351cm -1 、1052cm -1 : secondary-OH is present; 3328cm -1 : -a NH-narrow peak is present; 1770cm -1 : ester-C = O present; 943cm -1 、824cm -1 : epoxy groups are present and weakened; 744cm -1 : -C-Cl is present;
(6) Adding 1mol of phthalic anhydride and 1.4mol of mercaptoethanol into 300mL of dimethyl sulfoxide, heating to 175 ℃ under the protection of nitrogen, stirring for reaction for 3 hours, cooling, standing, vacuum concentrating, dissolving the concentrate into 300mL of ethyl acetate, adding 200mL of deionized water, stirring for 10 minutes, standing for layering, taking an organic phase, drying with 50g of anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product IV, wherein the infrared data of the intermediate product IV is as follows: 1250cm -1 : the anhydride disappears; 3225cm -1 : -OH (carboxyl) is present; 1719cm -1 : -C = O present; 3024cm -1 : a benzene ring C-H exists; 2551cm -1 : -SH is present;
(7) Dissolving 0.307g of the intermediate product IV in 40mL of N, placing N-dimethylformamide in a constant pressure dropping funnel to obtain a solution C;
(8) Placing 2.785g of intermediate product III, 0.05g of N, N-dimethylbenzylamine and 50mL of N, N-dimethylformamide into a three-neck flask, dropwise adding the solution C under stirring, stirring at 120 ℃ for reacting for 4h after the dropwise adding is finished, then cooling the temperature of a reaction system to room temperature, concentrating, adding 50mL of methanol, stirring, filtering, collecting insoluble substances, and drying in vacuum at 60 ℃ for 4h to obtain a blending modifier (a =465, b =24 and C = 45), wherein the infrared data of the blending modifier are as follows: 3225cm -1 : -OH (carboxyl) disappearance; 3351cm -1 、1052cm -1 : presence of secondary-OH；3328cm -1 : -a NH-narrow peak is present; 1769cm -1 : ester-C = O present; 943cm -1 、824cm -1 : epoxy groups are present; 3024cm -1 : a benzene ring C-H exists; 2551cm -1 : -SH is present; 744cm -1 : -C-Cl.
Comparative example 1 the same as example 1 except that the homemade blending modifier of the present invention was not added in comparative example 1.
Comparative example 2 the same as example 1 except that the PVC/TPU blend material system composition of comparative example 2, in parts by weight, was as follows:
the hydroxyl vinyl chloride-vinyl acetate copolymer is hydroxyl ternary vinyl chloride-vinyl acetate copolymer LPOH.
Comparative example 3 the same as example 1 except that the PVC/TPU blend material system composition of comparative example 3 in parts by weight was as follows:
comparative example 4 is the same as example 1 except that the PVC/TPU blend material system composition of comparative example 4, in parts by weight, was as follows:
comparative example 5 the same as example 1 except that the PVC/TPU blend material system composition of comparative example 5, in parts by weight, was comprised of:
performance test
According to the formula amount, the PVC/TPU blending material system compositions obtained in examples 1-11 and comparative examples 1-4 of the invention are respectively and uniformly mixed, plasticated on a double-roller open mill for 10min at 195 ℃, transferred to a flat vulcanizing machine, pressed into sheets at 195 ℃, and set for dwell time of 2min to obtain the PVC/TPU blending sheets. The PVC/TPU blended sheets obtained in examples 1 to 7 of the present invention and comparative examples 1 to 4 were subjected to the relevant performance tests, and the specific test results are shown in Table 1 and Table 1 below:
the specific test method is as follows:
(1) Apparent color: and (5) visual inspection. The sample was taken out of the press and observed for color change. Apparent color representation method: "5" is the lightest, i.e., optimal, color; "1" is the darkest (yellow) color, i.e., the worst.
(2) Elongation at break, tensile strength test: reference is made to GB/T1040-2006. The sample preparation is carried out on a 5A dumbbell type 4X 75 cutter on a universal tester, the loading rate is 50mm/min, the testing temperature is 23 ℃, and the testing data is the average value of 5 parallel samples.
(3) Shore hardness: reference is made to GB/T2411-2008.
(4) Migration performance: and (3) placing the PVC film in an ultraviolet light aging test box for 20 days, taking out, leaching the PVC film with acetonitrile, taking leaching liquid, measuring an ultraviolet-visible spectrum, and setting the wavelength to be in a range of 200-500 nm. The expression method of the migration effect is as follows: 5 is the lowest molar absorption coefficient, namely the optimal mobility; 1 is the highest molar absorption coefficient, i.e. the worst migration.
(5) And (3) gelation: dissolving 1.0000g sample tablet in THF for 24 hr, observing the dissolution state, and keeping the shape or skeleton as OK; complete dissolution is denoted as "NG".
(6) Heat shrinkage ε: cutting the sample into small blocks with 23 × 10mm by using a microtome, measuring the initial length (marked as L0) of each small block by using a vernier caliper, well registering, putting the sample into an incubator at 50 ℃ for heating for 6h, taking out the sample after heating is finished, cooling the sample to room temperature, testing the length (marked as Lt) again,
ε＝[(L0-Lt)/L0]×100％。
TABLE 1
First, as can be seen from table 1, the optimum amount ratio of the components in examples 1 to 5 of the present invention is example 1. The concrete expression is as follows: when the blending modifier is too little, the degree of reaction crosslinking between the blending modifier and a PVC/TPU material system is insufficient, and PVC and TPU have certain phase separation, so that the mechanical property is slightly poor; when the blending modifier is excessive, the excessive blending modifier can act as a plasticizer in the system after the blending modifier is fully crosslinked with a PVC/TPU system, and finally the tensile strength is reduced.
Example 1 compared to comparative examples 1-3, example 1 had superior mechanical properties and apparent color properties due to: the self-made blending modifier simultaneously contains structures such as vinyl chloride-vinyl acetate resin, ester group, epoxy group, carbamate, aliphatic chain, hydroxyl group, sulfydryl group and the like, and has excellent dispersibility, plasticity, auxiliary stability and low migration in a PVC/TPU material system.
Example 1 also had superior low migration, gelation properties and heat shrinkage compared to comparative examples 1-3, due to: in the embodiment 1, the macromolecular chains of the blending modifier and the PVC resin form chain entanglement among molecular chains in the processing process, so that the mobility is reduced; the mercapto structure of the blending modifier can enable the modifier to be bonded into a PVC molecular chain, and the mobility is further improved; in addition, the blending modifier has a similar structure with TPU, and has excellent compatibility between the two; the polyhydroxy structure of the blending modifier can form hydrogen bonds with carbamate in TPU, so that the compatibility between material systems is further improved, and the mobility of the blending modifier is reduced; the blending modifier can also be used as a crosslinking agent to 'hoop' the TPU elastomer, and has the advantage of improving the dimensional stability of the material.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. The PVC/TPU blending material system composition is characterized by comprising the following components in parts by weight:
2. the PVC/TPU blend material system composition of claim 1, wherein the blend modifier is prepared by the steps of:
(1) Dissolving 1g of hydroxychlorovinyl acetate resin in 50mL of methyl isobutyl ketone and placing the solution in a constant pressure dropping funnel to obtain solution A;
(2) Dissolving 0.237-0.302g of diisocyanate and 0.1-1mg of catalyst A in 300mL of methyl isobutyl ketone, placing the mixture in a reactor, heating the temperature in the reactor to 60-90 ℃, starting dropwise adding the solution A under magnetic stirring, then stirring a reaction system, keeping the temperature, reacting for 1-3 hours, standing, and cooling to room temperature to obtain a solution containing an intermediate product I;
(3) Adding 0.102-0.123g of hydroxy acid into the solution containing the intermediate product I, then heating the temperature of a reaction system to 40-80 ℃, stirring for reacting for 1-3h, standing after the reaction is finished, distilling under reduced pressure, concentrating, adding 400mL of ethyl acetate for dissolving, adding 300mL of deionized water into the solution system, stirring for 10min, standing for layering, taking an organic phase, drying with 55g of anhydrous sodium sulfate, filtering, performing rotary evaporation, and performing vacuum drying for 4h at 60 ℃ to obtain an intermediate product II;
(4) Dissolving 1.339-1.425g of intermediate product II in 50mL of N, placing N-dimethylformamide in a constant pressure dropping funnel to obtain a solution B;
(5) Placing 1.36g of epoxidized soybean oil, 0.02g of catalyst B and 40mL of N, N-dimethylformamide into a three-neck flask, heating to 100-130 ℃, dropwise adding the liquid B under stirring, stirring after dropwise adding, keeping the temperature for reaction for 1-3 hours, cooling the temperature of a reaction system to room temperature after reaction, distilling under reduced pressure, adding 50mL of isopropanol, stirring, filtering, collecting insoluble substances, and drying at 60 ℃ for 4 hours in vacuum to obtain an intermediate product III;
(6) Adding 1mol of phthalic anhydride and 1.2-1.5mol of mercaptoethanol into 300mL of dimethyl sulfoxide, heating to 155-180 ℃ under the protection of nitrogen, stirring for reacting for 2-5h, cooling, standing, vacuum concentrating, dissolving the concentrate into 300mL of ethyl acetate, adding 200mL of deionized water, stirring for 10min, standing for layering, taking an organic phase, drying with 50g of anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product IV;
(7) Dissolving 0.307g of the intermediate product IV in 40mL of N, placing N-dimethylformamide in a constant pressure dropping funnel to obtain a solution C;
(8) Placing 2.699-2.785g of intermediate product III, 0.05g of catalyst B and 50mL of N, N-dimethylformamide into a three-neck flask, beginning to stir and dropwise add the solution C, stirring and reacting for 2-5h at 110-135 ℃ after dropwise addition is finished, then cooling the temperature of a reaction system to room temperature, concentrating, adding 50mL of methanol, stirring, filtering, collecting insoluble substances, and vacuum drying for 4h at 60 ℃ to obtain the blending modifier.
3. The PVC/TPU blend system composition of claim 2, wherein said diisocyanate comprises toluene diisocyanate or isophorone diisocyanate.
4. The PVC/TPU blend material system composition of claim 2, wherein the hydroxy acid comprises glycolic acid or lactic acid.
5. The PVC/TPU blended material system composition as defined in claim 2, wherein the catalyst a comprises at least one of dibutyltin dilaurate, stannous octoate, triethylenediamine, or triethylamine.
6. The PVC/TPU blend material system composition of claim 1 wherein said catalyst B comprises at least one of triphenylphosphine, tetrabutylammonium bromide, or N, N-dimethylbenzylamine.
7. The PVC/TPU blended material system composition of claim 1, wherein said heat stabilizer comprises at least one of an organotin-based heat stabilizer, a calcium-zinc complex heat stabilizer, and a phosphite-based heat stabilizer.
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