CN115746539B - PVC/TPU blend material system composition - Google Patents
PVC/TPU blend material system composition Download PDFInfo
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- CN115746539B CN115746539B CN202211484547.4A CN202211484547A CN115746539B CN 115746539 B CN115746539 B CN 115746539B CN 202211484547 A CN202211484547 A CN 202211484547A CN 115746539 B CN115746539 B CN 115746539B
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- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 66
- 239000003607 modifier Substances 0.000 claims abstract description 57
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 108
- 238000003756 stirring Methods 0.000 claims description 87
- 239000013067 intermediate product Substances 0.000 claims description 81
- 238000006243 chemical reaction Methods 0.000 claims description 55
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 54
- 238000001914 filtration Methods 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000001291 vacuum drying Methods 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 26
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 claims description 25
- 238000010438 heat treatment Methods 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
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- DLZPQJDDVWPHNU-UHFFFAOYSA-N C(C)(=O)OC=C.OC=CCl Chemical compound C(C)(=O)OC=C.OC=CCl DLZPQJDDVWPHNU-UHFFFAOYSA-N 0.000 claims description 17
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 14
- 238000010025 steaming 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
- 239000012760 heat stabilizer Substances 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
- 238000003760 magnetic stirring Methods 0.000 claims description 8
- 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
- 239000007788 liquid Substances 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
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 1
- -1 polyethylene Polymers 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 125000003700 epoxy group Chemical group 0.000 abstract description 19
- 239000004014 plasticizer Substances 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 8
- 229920005989 resin Polymers 0.000 abstract description 8
- 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
- 230000008901 benefit Effects 0.000 abstract description 6
- 125000004185 ester group Chemical group 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 229920000728 polyester Polymers 0.000 abstract description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 abstract description 5
- 229920001971 elastomer Polymers 0.000 abstract description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- LZBCVRCTAYKYHR-UHFFFAOYSA-N acetic acid;chloroethene Chemical compound ClC=C.CC(O)=O LZBCVRCTAYKYHR-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
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 abstract description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 45
- 229920000915 polyvinyl chloride Polymers 0.000 description 44
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 38
- 229920002803 thermoplastic polyurethane Polymers 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
- 239000012948 isocyanate Substances 0.000 description 14
- 238000004090 dissolution Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 150000008064 anhydrides Chemical class 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 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
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification 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
- 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
- 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
- 229920001577 copolymer Polymers 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
- 238000011068 loading method Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 239000008029 phthalate plasticizer Substances 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
- 238000010998 test method Methods 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 phthalate plasticizers are added to promote the compatibility of the polyester TPU and the PVC in the blending process, the phthalate micromolecular plasticizers are easy to migrate and separate out to the surface of the blended product, the service life of the blended product is shortened, and potential threat is formed to human health. 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-acetate resin as a main chain, and a branched chain contains ester groups, epoxy groups, carbamate, long carbon chains of fat, hydroxyl groups, mercapto groups and other structures, has good compatibility with TPU and PVC, has the functions of a compatilizer, a plasticizer and a stabilizer, and can also be used as a cross-linking agent to clamp TPU elastomer, so that the PVC/TPU blending material system composition has the advantage of improving the dimensional stability of materials.
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 universal plastic, has low price, outstanding advantages and large yield, and is widely used in various industries of national economy. However, the soft PVC needs to be added with a large amount of plasticizer with low molecular weight to reduce the hardness, so that the material has the defects of poor elasticity, easy plastic deformation, large mechanical property loss, poor durability and the like.
The polyester Thermoplastic Polyurethane (TPU) has the high elasticity of rubber and the high hardness of plastic, and also has excellent wear resistance, low temperature resistance, chemical corrosion resistance and excellent weather resistance, so that the mechanical property, elasticity and thermal stability of the PVC can be effectively improved by blending the TPU with the PVC, and the flame retardance, corrosion resistance and other aspects of the TPU can be improved.
Studies have shown that PVC has a solubility parameter of 9.5 to 10.8 and tpu has a solubility parameter of about 10, with the possibility of blending compatibility between the two; but exhibit incompatibility when the difference in solubility parameters is greater than 0.5. In the process of blending PVC/TPU (polyester type), a phthalate plasticizer with small molecular weight is usually added to promote the compatibility of the polyester type TPU and PVC, however, the small molecular plasticizer is easy to migrate and separate out to the surface of a blended product, so that the service life of the blended product is shortened, and potential threat to human health is formed.
Disclosure of Invention
The problems in the prior art are: when phthalate plasticizers are added to promote the compatibility of the polyester TPU and the PVC in the blending process, the phthalate micromolecular plasticizers are easy to migrate and separate out to the surface of the blended product, the service life of the blended product is shortened, and potential threat is formed to human health.
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) 1g of hydroxy-vinyl chloride-acetate copolymer is dissolved in 50mL of methyl isobutyl ketone and placed 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 into a reactor, heating the temperature in the reactor to 60-90 ℃, starting to dropwise add the solution A under magnetic stirring, stirring and preserving the temperature of a reaction system for 1-3h, 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 a solution containing an intermediate product I, then raising the temperature of a reaction system to 40-80 ℃, stirring and reacting for 1-3h, standing, 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 and layering, taking an organic phase, drying with 55g of anhydrous sodium sulfate, filtering, steaming in a rotary mode, and vacuum drying at 60 ℃ for 4h to obtain an intermediate product II;
(4) 1.339-1.425g of intermediate II is dissolved in 50mL of N, N-dimethylformamide and placed in a constant pressure dropping funnel to obtain 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 B liquid under stirring, stirring and preserving heat for 1-3h after the dropwise adding is completed, cooling the temperature of a reaction system to room temperature after the reaction is completed, distilling under reduced pressure, adding 50mL of isopropanol, stirring, filtering, collecting insoluble matters, and vacuum drying at 60 ℃ for 4h 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 and reacting for 2-5h, cooling, standing, concentrating in vacuum, dissolving the concentrate in 300mL of ethyl acetate, adding 200mL of deionized water, stirring for 10min, standing and layering, taking an organic phase, drying with 50g of anhydrous sodium sulfate, filtering, and steaming in a rotary manner to obtain an intermediate product IV;
(7) Dissolving 0.307g of intermediate product IV in 40mL of N, N-dimethylformamide, and placing 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, dropwise adding the solution C while stirring, stirring at 110-135 ℃ for 2-5h after the dropwise adding is completed, cooling the temperature of a reaction system to room temperature, concentrating, adding 50mL of methanol, stirring, filtering, collecting insoluble matters, and vacuum drying at 60 ℃ for 4h to obtain the blending modifier.
In particular, the diisocyanate comprises toluene diisocyanate or isophorone diisocyanate.
Specifically, the hydroxy acid includes glycolic acid or lactic acid.
Specifically, the catalyst A comprises at least one of dibutyl tin 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 ester heat stabilizer.
Advantageous effects
(1) The self-made blending modifier is added into the PVC/TPU blending material system composition, the blending modifier takes the vinyl chloride-acetate resin as a main chain, and a branched chain contains ester groups, epoxy groups, carbamate, fatty long carbon chains, hydroxyl groups, mercapto groups and other structures, the main chain structure of the blending modifier is the vinyl chloride-acetate resin, the blending modifier has a highly similar structural unit with a PVC phase, and the blending modifier has excellent compatibility and dispersibility in the PVC resin according to similar compatibility;
(2) The ester group, the carbamate and the epoxy group in the self-made blending modifier structure have polarity, so that the strong polar acting force among PVC molecular chains can be relieved, and the plasticizing effect is achieved; in addition, the ester group and the epoxy group can capture HCl generated by PVC decomposition, and have excellent auxiliary stability effect;
(3) The self-made blending modifier has the advantages that a large number of long carbon chains of fat in the self-made blending modifier can provide plasticizing effect, so that the processing temperature of PVC is reduced;
(4) The mercapto in the self-made blending modifier structure can react with double bonds formed in the PVC degradation process to prevent the PVC from changing color and deteriorating, and has excellent thermal stability; meanwhile, the PVC is linked into the PVC through chemical bonds, so that the problem of migration and precipitation in the process of processing and using is further avoided;
(5) The self-made blending modifier provided by the invention has the advantages that the macromolecular chains and the PVC resin form chain entanglement among the molecular chains in the processing process, the pre-plasticizing is facilitated, and the low mobility of the self-made blending modifier is effectively ensured;
(6) The self-made blending modifier structure contains ester groups, carbamate and polyhydroxy structures, is similar to the TPU structure, has good compatibility, and can form hydrogen bonds with carbamate in the TPU, so that the compatibility is further improved;
(7) The self-made blending modifier is compatible with TPU and PVC, has the functions of the compatilizer, the plasticizer and the stabilizer, can be used as a cross-linking agent to clamp TPU elastomer, and has the advantage of improving the dimensional stability of the material.
Detailed Description
The TPU used in the following examples and comparative examples of the present invention is a smoke-counter Wanht-1565 IC polyurethane elastomer.
Example 1
The PVC/TPU blend material system composition comprises the following components in parts by weight:
the blending modifier is prepared according to the following steps:
(1) 1g of hydroxy-vinyl chloride-vinyl acetate copolymer is dissolved in 50mL of methyl isobutyl ketone and placed in a constant pressure dropping funnel to obtain a solution A, wherein the hydroxy-vinyl chloride-vinyl acetate copolymer is hydroxy ternary vinyl chloride-vinyl acetate copolymer LPOH;
(2) 0.302g of isophorone diisocyanate and 0.1mg of dibutyltin dilaurate are dissolved in 300mL of methyl isobutyl ketone and placed in a reactor, the temperature in the reactor is raised to 70 ℃, the solution A is started to be dropwise added under magnetic stirring, then the reaction system is stirred, kept warm and reacted for 3 hours, and the mixture is left stand and cooled to room temperature, so that a solution containing an intermediate product I is obtained, wherein the infrared data of the intermediate product 1 are as follows: 3328cm -1 : -NH-narrow peaks are present; 2275cm -1 : 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 and reacting for 3 hours, standing, distilling under reduced pressure, concentrating, adding 400mL of ethyl acetate for dissolution, adding 300mL of deionized water into the solution system, stirring for 10 minutes, standing and layering, taking an organic phase, drying with 55g of anhydrous sodium sulfate, filtering, steaming in a rotary manner, and 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 carboxyl groups; 3328cm -1 : -NH-narrow peaks are present and enhanced; 2275cm -1 : the isocyanate radical disappears; 1768cm -1 : ester-c=o present; 744cm -1 : -C-Cl is present;
(4) 1.425g of intermediate II is dissolved in 50mL of N, N-dimethylformamide and placed 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 and preserving heat for 2h after the dropwise adding is completed, cooling the temperature of a reaction system to room temperature after the reaction is completed, distilling under reduced pressure, adding 50mL of isopropanol, stirring, filtering, collecting insoluble matters, and 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 : the carboxyl group disappears; 3351cm -1 、1052cm -1 : secondary-OH 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) 1mol of phthalic anhydride and 1.4mol of mercaptoethanol are added into 300mL of dimethyl sulfoxide, the mixture is heated to 165 ℃ under the protection of nitrogen, stirred and reacted for 4 hours, cooled, stood still, concentrated in vacuum, the concentrate is dissolved in 300mL of ethyl acetate, 200mL of deionized water is added, stirred for 10 minutes, stood still and layered, an organic phase is taken and dried by 50g of anhydrous sodium sulfate, filtered and distilled soon, and an intermediate product IV is obtained, and infrared data of the intermediate product IV are as follows: 1250cm -1 : the anhydride disappears; 3225cm -1 : -OH (carboxyl) present; 1719cm -1 : -c=o present; 3024cm -1 : benzene ring C-H exists; 2551cm -1 : -SH is present;
(7) Dissolving 0.307g of intermediate product IV in 40mL of N, N-dimethylformamide, and placing in a constant pressure dropping funnel to obtain a solution C;
(8) 2.785g of an intermediate product III, 0.05g of N, N-dimethylbenzylamine and 50mL of N, N-dimethylformamide are placed in a three-neck flask, dropwise adding of a C solution is started while stirring, after the dropwise adding is completed, stirring is performed at 110 ℃ for 3 hours, then the temperature of a reaction system is reduced to room temperature, concentration is performed, 50mL of methanol is added, stirring is performed, filtration is performed, insoluble substances are collected, vacuum drying is performed at 60 ℃ for 4 hours, and a blending modifier (a=422, b=20 and c=40) is obtained, wherein the infrared data of the blending modifier are as follows: 3225cm -1 : -OH (carboxyl) disappeared; 3351cm -1 、1052cm -1 : secondary-OH present; 3328cm -1 : -NH-narrow peaks are present; 1769cm -1 : ester-c=o present; 943cm -1 、824cm -1 : the epoxy group is present; 3024cm -1 : benzene ring C-H exists; 2551cm -1 : -SH is present; 744cm -1 : -C-Cl is present.
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 the same as example 1 was used, except that the blending modifier was added in an amount of 1 part by weight in example 4.
Example 5 the same as example 1, except that the blending modifier was added in an amount of 5 parts by weight in example 5.
Example 6
The PVC/TPU blend material system composition comprises the following components in parts by weight:
the blending modifier is prepared according to the following steps:
(1) 1g of hydroxy-vinyl chloride-vinyl acetate copolymer is dissolved in 50mL of methyl isobutyl ketone and placed in a constant pressure dropping funnel to obtain solution A, wherein the hydroxy-vinyl chloride-vinyl acetate copolymer is hydroxy ternary vinyl chloride-vinyl acetate copolymer LPOH;
(2) 0.237g of toluene-2, 4-diisocyanate and 0.1mg of dibutyltin dilaurate are dissolved in 300mL of methyl isobutyl ketone and placed in a reactor, the temperature in the reactor is increased to 60 ℃, the solution A is started to be dropwise added under magnetic stirring, then the reaction system is stirred, kept warm and reacted for 3 hours, and the mixture is kept stand and cooled to room temperature, so that a solution containing an intermediate product I is obtained, wherein the infrared data of the intermediate product I are as follows: 3328cm -1 : -NH-narrow peaks are present; 3058cm -1 : benzene ring C-H exists; 2275cm -1 : the presence of isocyanate; 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 40 ℃, stirring and reacting for 3 hours, standing, distilling under reduced pressure, concentrating, adding 400mL of ethyl acetate for dissolution, adding 300mL of deionized water into the solution system, stirring for 10 minutes, standing and layering, taking an organic phase, drying with 55g of anhydrous sodium sulfate, filtering, steaming in a rotating way, and vacuum drying for 4 hours at 60 ℃ 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 carboxyl groups; 3328cm -1 : -NH-narrow peaks are present and enhanced; 3058cm -1 : benzene ring C-H exists; 2275cm -1 : the isocyanate radical disappears; 1768cm -1 : ester-c=o present; 744cm -1 : -C-Cl is present;
(4) 1.339g of intermediate II was dissolved in 50mL of N, N-dimethylformamide and placed in a constant pressure dropping funnel to obtain solution B;
(5) 1.36g of epoxidized soybean oil, 0.02g of N, N-dimethylbenzylamine and 40mL of N, N-dimethylformamide were placed in a three-necked flask,heating to 100 ℃, dropwise adding the solution B under stirring, stirring and preserving heat for 3 hours after the dropwise adding is completed, cooling the temperature of a reaction system to room temperature after the reaction is completed, distilling under reduced pressure, adding 50mL of isopropanol, stirring, filtering, collecting insoluble substances, and 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 : the carboxyl group disappears; 3351cm -1 、1052cm -1 : secondary-OH present; 3328cm -1 : -NH-narrow peaks are present; 3058cm -1 : 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 and reacting for 3 hours, cooling, standing, concentrating in vacuum, dissolving the concentrate into 300mL of ethyl acetate, adding 200mL of deionized water, stirring for 10 minutes, standing and layering, drying an organic phase by using 50g of anhydrous sodium sulfate, filtering, and steaming in a rotary manner 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) present; 1719cm -1 : -c=o present; 3024cm -1 : benzene ring C-H exists; 2551cm -1 : -SH is present;
(7) Dissolving 0.307g of intermediate product IV in 40mL of N, N-dimethylformamide, and placing in a constant pressure dropping funnel to obtain a solution C;
(8) Placing 2.699g of intermediate III, 0.05g of N, N-dimethylbenzylamine and 50mL of N, N-dimethylformamide into a three-neck flask, dropwise adding a C solution while stirring, stirring at 110 ℃ for reaction for 5 hours after dropwise adding is completed, then cooling the temperature of a reaction system to room temperature, concentrating, adding 50mL of methanol, stirring, filtering, collecting insoluble matters, and vacuum drying at 60 ℃ for 4 hours to obtain a blending modifier (a=422, b=20, c=40), wherein the infrared data of the blending modifier are as follows: 3225cm -1 : -OH (carboxyl) disappeared; 3351cm -1 、1052cm -1 : secondary-OH present; 3328cm -1 : -NH-narrow peaks are present; 1769cm -1 : ester-c=o present; 943cm -1 、824cm -1 : the epoxy group is present; 3024cm -1 、3058cm -1 : benzene ring C-H exists; 2551cm -1 : -SH is present; 744cm -1 : -C-Cl is present.
Example 7
The PVC/TPU blend material system composition comprises the following components in parts by weight:
the blending modifier is prepared according to the following steps:
(1) 1g of hydroxy-vinyl chloride-vinyl acetate copolymer is dissolved in 50mL of methyl isobutyl ketone and placed in a constant pressure dropping funnel to obtain solution A, wherein the hydroxy-vinyl chloride-vinyl acetate copolymer is hydroxy ternary vinyl chloride-vinyl acetate copolymer LPOH;
(2) Dissolving 0.302g of isophorone diisocyanate and 0.1mg of stannous octoate in 300mL of methyl isobutyl ketone, placing the solution into a reactor, heating the temperature in the reactor to 70 ℃, starting to dropwise add the solution A under magnetic stirring, stirring the reaction system, keeping the temperature 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 : -NH-narrow peaks are present; 2275cm -1 : the presence of isocyanate; 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 and reacting for 2 hours, standing, distilling under reduced pressure, concentrating, adding 400mL of ethyl acetate for dissolution, adding 300mL of deionized water into the solution system, stirring for 10 minutes, standing and layering, taking an organic phase, drying with 55g of anhydrous sodium sulfate, filtering, steaming in a rotary manner, and 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 carboxyl groups; 3328cm -1 : -NH-narrow peaks are present and enhanced; 2275cm -1 : the isocyanate radical disappears; 1768cm -1 : ester-c=o present; 744cm -1 : -C-Cl is present;
(4) 1.404g of intermediate II is dissolved in 50mL of N, N-dimethylformamide and placed 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 a solution B under stirring, stirring and preserving heat for 1h after the dropwise adding is completed, cooling the temperature of a reaction system to room temperature after the reaction is completed, distilling under reduced pressure, adding 50mL of isopropanol, stirring, filtering, collecting insoluble matters, and 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 : the carboxyl group disappears; 3351cm -1 、1052cm -1 : secondary-OH 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) 1mol of phthalic anhydride and 1.5mol of mercaptoethanol are added into 300mL of dimethyl sulfoxide, the mixture is heated to 155 ℃ under the protection of nitrogen, stirred and reacted for 5 hours, cooled, stood still, concentrated in vacuum, the concentrate is dissolved in 300mL of ethyl acetate, 200mL of deionized water is added, stirred for 10 minutes, stood still and layered, an organic phase is taken and dried by 50g of anhydrous sodium sulfate, filtered and steamed in a rotating way, and an intermediate product IV is obtained, and infrared data of the intermediate product IV are as follows: 1250cm -1 : the anhydride disappears; 3225cm -1 : -OH (carboxyl) present; 1719cm -1 : -c=o present; 3024cm -1 : benzene ring C-H exists; 2551cm -1 : -SH is present;
(7) Dissolving 0.307g of intermediate product IV in 40mL of N, N-dimethylformamide, and placing in a constant pressure dropping funnel to obtain a solution C;
(8) 2.764g of intermediate III, 0.05g of triphenylphosphine and 50mL of N, N-dimethylformamide are placed in a three-neck flask, C liquid is dropwise added while stirring, after the dropwise addition is completed, stirring is carried out at 135 ℃ for 2 hours, then the temperature of a reaction system is reduced to room temperature, concentration is carried out, 50mL of methanol is added, stirring and filtration are carried out, insoluble substances are collected, vacuum drying is carried out at 60 ℃ for 4 hours, and the infrared data of the blending modifier (a=422, b=20 and c=40) are obtained: 3225cm -1 : -OH (carboxyl) disappeared; 3351cm -1 、1052cm -1 : secondary-OH present; 3328cm -1 : -NH-narrow peaks are present; 1769cm -1 : ester-c=o present; 943cm -1 、824cm -1 : the epoxy group is present; 3024cm -1 : benzene ring C-H exists; 2551cm -1 : -SH is present; 744cm -1 : -C-Cl is present.
Example 8
The PVC/TPU blend material system composition comprises the following components in parts by weight:
the blending modifier is prepared according to the following steps:
(1) 1g of hydroxy-vinyl chloride-vinyl acetate copolymer is dissolved in 50mL of methyl isobutyl ketone and placed in a constant pressure dropping funnel to obtain solution A, wherein the hydroxy-vinyl chloride-vinyl acetate copolymer is hydroxy ternary vinyl chloride-vinyl acetate copolymer UMOH;
(2) 0.237g of toluene-2, 6-diisocyanate and 0.5mg of triethylenediamine are dissolved in 300mL of methyl isobutyl ketone and placed in a reactor, the temperature in the reactor is increased to 90 ℃, the solution A is started to be dropwise added under magnetic stirring, then the reaction system is stirred and kept at a temperature for 3 hours for reaction, the mixture is left stand and cooled to room temperature, and a solution containing an intermediate product I is obtained, wherein the infrared data of the intermediate product I are as follows: 3328cm -1 : -NH-narrow peaks are present; 3058cm -1 : benzene ring C-H exists; 2275cm -1 : 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 and reacting for 1h, standing, 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 and layering, taking an organic phase, drying with 55g of anhydrous sodium sulfate, filtering, steaming in a rotary manner, and 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 : carboxyl groupPresence; 3328cm -1 : -NH-narrow peaks are present and enhanced; 3058cm -1 : benzene ring C-H exists; 2275cm -1 : the isocyanate radical disappears; 1768cm -1 : ester-c=o present; 744cm -1 : -C-Cl is present;
(4) 1.36g of intermediate II is dissolved in 50mL of N, N-dimethylformamide and placed 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 a solution B under stirring, stirring and preserving heat for 2 hours after the dropwise adding is completed, cooling the temperature of a reaction system to room temperature after the reaction is completed, distilling under reduced pressure, adding 50mL of isopropanol, stirring, filtering, collecting insoluble matters, and 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 : the carboxyl group disappears; 3351cm -1 、1052cm -1 : secondary-OH present; 3328cm -1 : -NH-narrow peaks are present; 3058cm -1 : 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) 1mol of phthalic anhydride and 1.2mol of mercaptoethanol are added into 300mL of dimethyl sulfoxide, the mixture is heated to 180 ℃ under the protection of nitrogen, stirred and reacted for 2 hours, cooled, stood still, concentrated in vacuum, the concentrate is dissolved in 300mL of ethyl acetate, 200mL of deionized water is added, stirred for 10 minutes, stood still and layered, an organic phase is taken and dried by 50g of anhydrous sodium sulfate, filtered and distilled soon, and an intermediate product IV is obtained, and infrared data of the intermediate product IV are as follows: 1250cm -1 : the anhydride disappears; 3225cm -1 : -OH (carboxyl) present; 1719cm -1 : -c=o present; 3024cm -1 : benzene ring C-H exists; 2551cm -1 : -SH is present;
(7) Dissolving 0.307g of intermediate product IV in 40mL of N, N-dimethylformamide, and placing in a constant pressure dropping funnel to obtain a solution C;
(8) 2.72g of intermediate III, 0.05g of tetrabutylammonium bromide, 50mL of N, N-dimethylformamide were placed in a three-necked flask, starting withDropwise adding the solution C while stirring, after dropwise adding, stirring at 130 ℃ for 2 hours, cooling the temperature of a reaction system to room temperature, concentrating, adding 50mL of methanol, stirring, filtering, collecting insoluble substances, and vacuum drying at 60 ℃ for 4 hours to obtain a blending modifier (a=465, b=24, c=45), wherein the infrared data of the blending modifier are as follows: 3225cm -1 : -OH (carboxyl) disappeared; 3351cm -1 、1052cm -1 : secondary-OH present; 3328cm -1 : -NH-narrow peaks are present; 1769cm -1 : ester-c=o present; 943cm -1 、824cm -1 : the epoxy group is present; 3024cm -1 、3058cm -1 : benzene ring C-H exists; 2551cm -1 : -SH is present; 744cm -1 : -C-Cl is present.
Example 9
The PVC/TPU blend material system composition comprises the following components in parts by weight:
the blending modifier is prepared according to the following steps:
(1) 1g of hydroxy-vinyl chloride-vinyl acetate copolymer is dissolved in 50mL of methyl isobutyl ketone and placed in a constant pressure dropping funnel to obtain solution A, wherein the hydroxy-vinyl chloride-vinyl acetate copolymer is hydroxy ternary vinyl chloride-vinyl acetate copolymer UMOH;
(2) 0.237g of toluene-2, 4-diisocyanate and 0.5mg of triethylamine are dissolved in 300mL of methyl isobutyl ketone and placed in a reactor, the temperature in the reactor is increased to 90 ℃, the solution A is started to be dropwise added under magnetic stirring, then the reaction system is stirred and kept at a temperature for 3 hours for reaction, the mixture is left stand and cooled to room temperature, and a solution containing an intermediate product I is obtained, wherein the infrared data of the intermediate product I are as follows: 3328cm -1 : -NH-narrow peaks are present; 3058cm -1 : benzene ring C-H exists; 2275cm -1 : the presence of isocyanate; 1768cm -1 : -c=o present; 744cm -1 : -C-Cl is present;
(3) Adding 0.102g of glycolic acid into the solution containing the intermediate product I, then heating the reaction system to 80 ℃, stirring and reacting 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 a solution system, stirring for 10min, standing for layering, taking an organic phase, drying with 55g of anhydrous sodium sulfate, filtering, rotary steaming, and 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 carboxyl groups; 3328cm -1 : -NH-narrow peaks are present and enhanced; 3058cm -1 : benzene ring C-H exists; 2275cm -1 : the isocyanate radical disappears; 1768cm -1 : ester-c=o present; 744cm -1 : -C-Cl is present;
(4) 1.339g of intermediate II was dissolved in 50mL of N, N-dimethylformamide and placed 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 a solution B under stirring, stirring and preserving heat for 1h after the dropwise adding is completed, cooling the temperature of a reaction system to room temperature after the reaction is completed, distilling under reduced pressure, adding 50mL of isopropanol, stirring, filtering, collecting insoluble matters, and 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 : the carboxyl group disappears; 3351cm -1 、1052cm -1 : secondary-OH present; 3328cm -1 : -NH-narrow peaks are present; 3058cm -1 : 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 and reacting for 2 hours, cooling, standing, concentrating in vacuum, dissolving the concentrate into 300mL of ethyl acetate, adding 200mL of deionized water, stirring for 10 minutes, standing and layering, drying an organic phase by using 50g of anhydrous sodium sulfate, filtering, and steaming in a rotary manner 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) present; 1719cm -1 : -c=o present; 3024cm -1 : benzene ring C-H exists; 2551cm -1 : -SH is present;
(7) Dissolving 0.307g of intermediate product IV in 40mL of N, N-dimethylformamide, and placing in a constant pressure dropping funnel to obtain a solution C;
(8) Placing 2.699g of intermediate III, 0.05g of triphenylphosphine and 50mL of N, N-dimethylformamide into a three-neck flask, dropwise adding a C solution while stirring, stirring at 135 ℃ for 2h after the dropwise adding is completed, cooling the temperature of a reaction system to room temperature, concentrating, adding 50mL of methanol, stirring, filtering, collecting insoluble substances, and vacuum-drying at 60 ℃ for 4h to obtain a blending modifier (a=465, b=24, c=45), wherein the infrared data of the blending modifier are as follows: 3225cm -1 : -OH (carboxyl) disappeared; 3351cm -1 、1052cm -1 : secondary-OH present; 3328cm -1 : -NH-narrow peaks are present; 1769cm -1 : ester-c=o present; 943cm -1 、824cm -1 : the epoxy group is present; 3024cm -1 、3058cm -1 : benzene ring C-H exists; 2551cm -1 : -SH is present; 744cm -1 : -C-Cl is present.
Example 10
The PVC/TPU blend material system composition comprises the following components in parts by weight:
the blending modifier is prepared according to the following steps:
(1) 1g of hydroxy-vinyl chloride-vinyl acetate copolymer is dissolved in 50mL of methyl isobutyl ketone and placed in a constant pressure dropping funnel to obtain solution A, wherein the hydroxy-vinyl chloride-vinyl acetate copolymer is hydroxy ternary vinyl chloride-vinyl acetate copolymer UMOH;
(2) 0.237g of toluene-2, 6-diisocyanate and 0.5mg of stannous octoate are dissolved in 300mL of methyl isobutyl ketone and placed in a reactor, the temperature in the reactor is increased to 90 ℃, the solution A is started to be dropwise added under the magnetic stirring, then the reaction system is stirred and kept at the temperature for 3 hours for reaction, the mixture is kept stand and cooled to the room temperature, the solution containing an intermediate product I is obtained, and infrared data are as follows: 3328cm -1 : -NH-narrow peaks are present; 3058cm -1 : benzene ring C-H exists; 2275cm -1 : the presence of isocyanate; 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 and reacting for 3 hours, standing, distilling under reduced pressure, concentrating, adding 400mL of ethyl acetate for dissolution, adding 300mL of deionized water into the solution system, stirring for 10 minutes, standing and layering, taking an organic phase, drying with 55g of anhydrous sodium sulfate, filtering, steaming in a rotating way, and vacuum drying for 4 hours at 60 ℃ to obtain an intermediate product II, wherein infrared data are as follows: 3392cm -1 、1751cm -1 : the presence of carboxyl groups; 3328cm -1 : -NH-narrow peaks are present and enhanced; 3058cm -1 : benzene ring C-H exists; 2275cm -1 : the isocyanate radical disappears; 1768cm -1 : ester-c=o present; 744cm -1 : -C-Cl is present;
(4) 1.229g of intermediate II is dissolved in 50mL of N, N-dimethylformamide and placed 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 solution B under stirring, stirring and preserving heat for 3h after the dropwise adding is completed, cooling the temperature of a reaction system to room temperature after the reaction is completed, distilling under reduced pressure, adding 50mL of isopropanol, stirring, filtering, collecting insoluble matters, and vacuum drying at 60 ℃ for 4h to obtain an intermediate product III, wherein the infrared data are as follows: 3392cm -1 、1751cm -1 : the carboxyl group disappears; 3351cm -1 、1052cm -1 : secondary-OH present; 3328cm -1 : -NH-narrow peaks are present; 3058cm -1 : 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 and reacting for 2 hours, cooling, standing, concentrating under vacuum, dissolving the concentrate in 300mL of ethyl acetate, adding 200mL of deionized water, stirring for 10 minutes, standing and layering, and taking an organic phase by using 50g of anhydrous sulfuric acidSodium is dried, filtered and rotary distilled to obtain intermediate IV, the infrared data is as follows: 1250cm -1 : the anhydride disappears; 3225cm -1 : -OH (carboxyl) present; 1719cm -1 : -c=o present; 3024cm -1 : benzene ring C-H exists; 2551cm -1 : -SH is present;
(7) Dissolving 0.307g of intermediate product IV in 40mL of N, N-dimethylformamide, and placing in a constant pressure dropping funnel to obtain a solution C;
(8) Placing 2.699g of intermediate III, 0.05g of N, N-dimethylbenzylamine and 50mL of N, N-dimethylformamide into a three-neck flask, dropwise adding a C solution 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 matters, and vacuum-drying 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) disappeared; 3351cm -1 、1052cm -1 : secondary-OH present; 3328cm -1 : -NH-narrow peaks are present; 1769cm -1 : ester-c=o present; 943cm -1 、824cm -1 : the epoxy group is present; 3024cm -1 、3058cm -1 : benzene ring C-H exists; 2551cm -1 : -SH is present; 744cm -1 : -C-Cl is present.
Example 11
The PVC/TPU blend material system composition comprises the following components in parts by weight:
the blending modifier is prepared according to the following steps:
(1) 1g of hydroxy-vinyl chloride-vinyl acetate copolymer is dissolved in 50mL of methyl isobutyl ketone and placed in a constant pressure dropping funnel to obtain solution A, wherein the hydroxy-vinyl chloride-vinyl acetate copolymer is hydroxy ternary vinyl chloride-vinyl acetate copolymer UMOH;
(2) 0.302g of isophorone diisocyanate, 0.5mg of dibutyltin dilaurate were dissolved in 300mL of methyl isobutyl ketone and placed in a reactor, the temperature in the reactor was raised to 70℃and the reactor was opened under magnetic stirringDropwise adding the solution A, stirring the 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 infrared data of the intermediate product I are as follows: 3328cm -1 : -NH-narrow peaks are present; 2275cm -1 : 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 and reacting for 2 hours, standing, distilling under reduced pressure, concentrating, adding 400mL of ethyl acetate for dissolution, adding 300mL of deionized water into the solution system, stirring for 10 minutes, standing and layering, taking an organic phase, drying with 55g of anhydrous sodium sulfate, filtering, steaming in a rotary manner, and 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 carboxyl groups; 3328cm -1 : -NH-narrow peaks are present and enhanced; 2275cm -1 : the isocyanate radical disappears; 1768cm -1 : ester-c=o present; 744cm -1 : -C-Cl is present;
(4) 1.425g of intermediate II is dissolved in 50mL of N, N-dimethylformamide and placed 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 and preserving heat for reaction for 1h after the dropwise adding is completed, cooling the temperature of a reaction system to room temperature after the reaction is completed, distilling under reduced pressure, adding 50mL of isopropanol, stirring, filtering, collecting insoluble matters, and 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 : the carboxyl group disappears; 3351cm -1 、1052cm -1 : secondary-OH 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) 1mol of phthalic anhydride and 1.4mol of mercaptoethanol are added into 300mL of dimethyl sulfoxide, and the mixture is heated to 175 ℃ under the protection of nitrogen and stirredStirring for reaction for 3h, cooling, standing, concentrating in vacuum, dissolving the concentrate in 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 steaming in a rotary manner 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) present; 1719cm -1 : -c=o present; 3024cm -1 : benzene ring C-H exists; 2551cm -1 : -SH is present;
(7) Dissolving 0.307g of intermediate product IV in 40mL of N, N-dimethylformamide, and placing in a constant pressure dropping funnel to obtain a solution C;
(8) 2.785g of an intermediate product III, 0.05g of N, N-dimethylbenzylamine and 50mL of N, N-dimethylformamide are placed in a three-neck flask, C liquid is dropwise added while stirring, after the dropwise addition is completed, stirring is performed at 120 ℃ for 4 hours, then the temperature of a reaction system is reduced to room temperature, concentration is performed, 50mL of methanol is added, stirring is performed, filtration is performed, insoluble substances are collected, and vacuum drying is performed at 60 ℃ for 4 hours, so that a blending modifier (a=465, b=24 and c=45) is obtained, wherein the infrared data of the blending modifier are as follows: 3225cm -1 : -OH (carboxyl) disappeared; 3351cm -1 、1052cm -1 : secondary-OH present; 3328cm -1 : -NH-narrow peaks are present; 1769cm -1 : ester-c=o present; 943cm -1 、824cm -1 : the epoxy group is present; 3024cm -1 : benzene ring C-H exists; 2551cm -1 : -SH is present; 744cm -1 : -C-Cl is present.
Comparative example 1 the same as example 1 was different in that the inventive homemade blending modifier was not added in comparative example 1.
Comparative example 2 the same as example 1, except that the PVC/TPU blend material system composition in comparative example 2 was composed as follows in parts by weight:
the hydroxy vinyl chloride-vinyl acetate resin is hydroxy ternary vinyl chloride-vinyl acetate resin LPOH.
Comparative example 3 the same as example 1, except that the PVC/TPU blend material system composition in comparative example 3 was composed as follows in parts by weight:
comparative example 4 the same as example 1, except that the PVC/TPU blend material system composition in comparative example 4 was composed as follows in parts by weight:
comparative example 5 the same as example 1, except that the PVC/TPU blend material system composition in comparative example 5 was composed as follows in parts by weight:
performance testing
According to the formula amount, the PVC/TPU blend material system compositions obtained in examples 1-11 and comparative examples 1-4 are respectively and uniformly mixed, plasticated for 10min on a two-roll open mill at 195 ℃, transferred to a flat vulcanizing machine, pressed into tablets at 195 ℃ and set for 2min to obtain the PVC/TPU blend sheet. The PVC/TPU blended sheets obtained in examples 1 to 7 and comparative examples 1 to 4 of the present invention were subjected to the relevant performance test, and the specific test results are shown in Table 1, the following Table 1:
the specific test method is as follows:
(1) Apparent color: visual inspection. After the sample was taken out from the press vulcanizer, the color change was observed. Apparent color representation method: "5" is the lightest color, i.e., optimal; "1" is the darkest (yellow), i.e., worst, color.
(2) Elongation at break, tensile strength test: reference is made to GB/T1040-2006. The sample preparation of the 5A dumbbell type 4X 75 type cutter is carried out on a universal testing machine, the loading rate is 50mm/min, the testing temperature is 23 ℃, and the average value of 5 parallel samples is taken as the testing data.
(3) Shore hardness: refer to GB/T2411-2008.
(4) Migration performance: placing the PVC film in an ultraviolet aging test box for 20 days, taking out, eluting the PVC film with acetonitrile, taking out the eluting solution, measuring ultraviolet-visible spectrum, and setting the wavelength to be in the range of 200-500 nm. The migration effect is expressed by the following steps: 5 is the lowest molar absorption coefficient, namely the optimal mobility; 1 is the molar absorption coefficient that is the largest, i.e. the worst mobility.
(5) Gelation: taking 1.0000g sample, dissolving in THF for 24h, observing the dissolution state, and keeping the shape or the skeleton existence as OK; complete dissolution was noted as "NG".
(6) Heat shrinkage epsilon: cutting the sample into small squares with the diameter of 23-10 mm by using a microtome, measuring the initial length (marked as L0) of each small square by using a vernier caliper, registering, then placing the sample into a constant temperature box with the temperature of 50 ℃ for heating for 6 hours, taking out the sample after heating, cooling the sample to room temperature, retesting the length (marked as Lt) of the sample,
ε＝[(L0-Lt)/L0]×100％。
TABLE 1
First, as can be seen from Table 1, in examples 1 to 5 of the present invention, the optimum amount ratio was example 1. The concrete steps are as follows: when the blending modifier is too little, the reaction crosslinking degree of the blending modifier and the PVC/TPU material system is insufficient, and the PVC and the TPU have certain phase separation, so that the mechanical property is slightly poor; when the blending modifier is too much, after the blending modifier is fully crosslinked with the PVC/TPU system, the excessive blending modifier plays a role of a plasticizer in the system, and finally the tensile strength is reduced.
Example 1 has superior mechanical properties and apparent color properties compared to comparative examples 1-3, because: the self-made blending modifier simultaneously contains structures such as vinyl chloride-vinyl acetate copolymer, ester group, epoxy group, carbamate, fatty chain, hydroxyl group, mercapto group and the like, and has excellent dispersibility, plasticity, auxiliary stability and low migration in a PVC/TPU material system.
Example 1 also has superior low migration, gelation properties and heat shrinkage compared to comparative examples 1-3, because: in the embodiment 1, macromolecular chains of the blending modifier and the PVC resin form chain entanglement among the molecular chains in the processing process, so that the mobility is reduced; the sulfhydryl structure of the blended modifier can bond the modifier into a PVC molecular chain, so that the mobility is further improved; in addition, the blending modifier has a similar structure with the TPU, and has excellent compatibility with the TPU; the polyhydroxy structure of the blending modifier can form hydrogen bonds with carbamate in the 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 cross-linking agent to "hoop" the TPU elastomer, and has the advantage of improving the dimensional stability of the material.
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (4)
1. The PVC/TPU blend material system composition is characterized by comprising the following components in parts by weight:
PVC 35 parts
TPU 65 parts
3 parts of blending modifier
1 to 1.5 parts of heat stabilizer
0.1-0.5 part of polyethylene wax;
the blending modifier is prepared according to the following steps:
(1) 1g of hydroxy-vinyl chloride-vinyl acetate copolymer is dissolved in 50mL of methyl isobutyl ketone and placed in a constant pressure dropping funnel to obtain a solution A, wherein the hydroxy-vinyl chloride-vinyl acetate copolymer is hydroxy ternary vinyl chloride-vinyl acetate copolymer LPOH;
(2) Dissolving 0.237-0.302g of diisocyanate and 0.1-1mg of catalyst A in 300mL of methyl isobutyl ketone, placing the mixture into a reactor, heating the temperature in the reactor to 60-90 ℃, starting to dropwise add the solution A under magnetic stirring, stirring and preserving the temperature of a reaction system for 1-3h, 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 a solution containing an intermediate product I, then raising the temperature of a reaction system to 40-80 ℃, stirring and reacting for 1-3h, standing, 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 and layering, taking an organic phase, drying with 55g of anhydrous sodium sulfate, filtering, steaming in a rotary mode, and vacuum drying at 60 ℃ for 4h to obtain an intermediate product II;
(4) 1.339-1.425g of intermediate II is dissolved in 50mL of N, N-dimethylformamide and placed in a constant pressure dropping funnel to obtain 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 B liquid under stirring, stirring and preserving heat for 1-3h after the dropwise adding is completed, cooling the temperature of a reaction system to room temperature after the reaction is completed, distilling under reduced pressure, adding 50mL of isopropanol, stirring, filtering, collecting insoluble matters, and vacuum drying at 60 ℃ for 4h 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 and reacting for 2-5h, cooling, standing, concentrating in vacuum, dissolving the concentrate in 300mL of ethyl acetate, adding 200mL of deionized water, stirring for 10min, standing and layering, taking an organic phase, drying with 50g of anhydrous sodium sulfate, filtering, and steaming in a rotary manner to obtain an intermediate product IV;
(7) Dissolving 0.307g of intermediate product IV in 40mL of N, N-dimethylformamide, and placing 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, dropwise adding a solution C while stirring, stirring at 110-135 ℃ for 2-5h after dropwise adding, cooling the temperature of a reaction system to room temperature, concentrating, adding 50mL of methanol, stirring, filtering, collecting insoluble matters, and vacuum drying at 60 ℃ for 4h to obtain a blending modifier;
the diisocyanate comprises toluene diisocyanate or isophorone diisocyanate;
the hydroxy acid includes glycolic acid or lactic acid.
2. A PVC/TPU blend material system composition according to claim 1, wherein the catalyst a comprises at least one of dibutyl tin dilaurate, stannous octoate, triethylenediamine or triethylamine.
3. A PVC/TPU blend material system composition according to claim 1, wherein the catalyst B comprises at least one of triphenylphosphine, tetrabutylammonium bromide or N, N-dimethylbenzylamine.
4. The PVC/TPU blend material system composition of claim 1, wherein the heat stabilizer comprises at least one of an organotin-based heat stabilizer, a calcium zinc composite heat stabilizer, and a phosphite-based heat stabilizer.
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| US5512651A (en) * | 1994-07-29 | 1996-04-30 | Minnesota Mining And Manufacturing Company | Strong carboxylic acid functional polyurethane polymers and blends thereof used in magnetic recording media |
| CN102391769A (en) * | 2011-09-14 | 2012-03-28 | 上海长润发涂料有限公司 | Novel poly urethane (PU) yellowing-resistant quick-drying open varnish |
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Effective date of registration: 20231024 Address after: 213000 No.1, dangli New District, Chaoyang village, Hengshanqiao Town, Wujin District, Changzhou City, Jiangsu Province Patentee after: Changzhou Weisheng Plastic Co.,Ltd. Address before: 213000 33 Gehu Middle Road, HUTANG Town, Wujin District, Changzhou City, Jiangsu Province Patentee before: CHANGZHOU VOCATIONAL INSTITUTE OF ENGINEERING |