CN116462657A - Thienyl rare earth stabilizer for PVC and preparation method thereof - Google Patents
Thienyl rare earth stabilizer for PVC and preparation method thereof Download PDFInfo
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- CN116462657A CN116462657A CN202310435373.0A CN202310435373A CN116462657A CN 116462657 A CN116462657 A CN 116462657A CN 202310435373 A CN202310435373 A CN 202310435373A CN 116462657 A CN116462657 A CN 116462657A
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- 239000003381 stabilizer Substances 0.000 title claims abstract description 71
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 63
- -1 Thienyl rare earth Chemical class 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 150000002602 lanthanoids Chemical group 0.000 claims abstract description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 59
- 238000003756 stirring Methods 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 37
- 239000013067 intermediate product Substances 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 32
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 20
- 239000000194 fatty acid Substances 0.000 claims description 20
- 229930195729 fatty acid Natural products 0.000 claims description 20
- 150000004665 fatty acids Chemical class 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 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 claims description 14
- AGZYNVVJQAOVRP-UHFFFAOYSA-N thiophene-3,4-diamine Chemical compound NC1=CSC=C1N AGZYNVVJQAOVRP-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 12
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 11
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000003287 bathing Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 238000010025 steaming Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- KRBFFJIZAKABSA-UHFFFAOYSA-N 2-bromooctadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(Br)C(O)=O KRBFFJIZAKABSA-UHFFFAOYSA-N 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- HXKXBCBZXXQPPD-UHFFFAOYSA-N 2-bromododecanoic acid Chemical compound CCCCCCCCCCC(Br)C(O)=O HXKXBCBZXXQPPD-UHFFFAOYSA-N 0.000 claims description 4
- DPRAYRYQQAXQPE-UHFFFAOYSA-N 2-bromohexadecanoic acid Chemical compound CCCCCCCCCCCCCCC(Br)C(O)=O DPRAYRYQQAXQPE-UHFFFAOYSA-N 0.000 claims description 4
- GBBKJNDQLLKTCX-UHFFFAOYSA-N 2-bromotetradecanoic acid Chemical compound CCCCCCCCCCCCC(Br)C(O)=O GBBKJNDQLLKTCX-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- GQZXYZIKUQUVKE-UHFFFAOYSA-N 2-bromo-3-methylpentanoic acid Chemical compound CCC(C)C(Br)C(O)=O GQZXYZIKUQUVKE-UHFFFAOYSA-N 0.000 claims description 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims 7
- 238000004519 manufacturing process Methods 0.000 claims 5
- 150000007513 acids Chemical class 0.000 claims 1
- 150000002910 rare earth metals Chemical class 0.000 abstract description 22
- 150000001408 amides Chemical class 0.000 abstract description 10
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract description 7
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 125000001931 aliphatic group Chemical group 0.000 abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 5
- 238000002845 discoloration Methods 0.000 abstract description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 abstract description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 73
- 229920000915 polyvinyl chloride Polymers 0.000 description 72
- 239000000463 material Substances 0.000 description 13
- 238000004040 coloring Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 9
- 239000012760 heat stabilizer Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- ISYWECDDZWTKFF-UHFFFAOYSA-N nonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)=O ISYWECDDZWTKFF-UHFFFAOYSA-N 0.000 description 8
- 230000002238 attenuated effect Effects 0.000 description 5
- 150000007942 carboxylates Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052746 lanthanum Inorganic materials 0.000 description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- 229930192474 thiophene Natural products 0.000 description 5
- 150000003577 thiophenes Chemical class 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000006298 dechlorination reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/30—Hetero atoms other than halogen
- C07D333/36—Nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention provides a thienyl rare earth stabilizer for PVC and a preparation method thereof, relating to the technical field of PVC processing aids; the molecular structure of the rare earth stabilizer simultaneously contains a double-molecular thiophene ring, carboxyl, amide, long aliphatic chain, beta-diketone and lanthanoid structure, so that the rare earth stabilizer has excellent thermal stability and light stability, can inhibit initial decomposition and discoloration of PVC, improves initial colorability of the rare earth stabilizer, and solves the problem of poor initial colorability of the rare earth stabilizer in the prior art.
Description
Technical Field
The invention relates to the technical field of PVC processing aids, in particular to a thienyl rare earth stabilizer for PVC and a preparation method thereof.
Background
Polyvinyl chloride (PVC) is one of five general plastics in the world and has been widely used in various fields such as chemical industry, construction, light industry, packaging, and cables. However, PVC is easily decomposed by dehydrochlorination during processing, seriously affecting PVC processability and mechanical properties, and thus a heat stabilizer must be added to PVC resin.
Lead salt stabilizers have been disabled due to toxicity issues. The main heat stabilizers at present comprise metal soap stabilizers and organic tin compounds; however, these stabilizers have disadvantages in terms of environmental pollution or high cost. The rare earth stabilizer is a novel stabilizer, has the advantages of high efficiency, no toxicity and the like, and is one of few heat stabilizer types meeting the environmental protection requirement.
In recent years, the hot trend of research on rare earth stabilizers has been raised; however, rare earth heat stabilizers have a disadvantage of poor initial coloring properties, and the initial coloring resistance has been conventionally solved by compounding with other auxiliary heat stabilizers.
Accordingly, it is an urgent need to provide a rare earth stabilizer having both high thermal stability and initial coloring resistance.
Disclosure of Invention
The invention aims to solve the technical problems that: in order to solve the problem of poor initial coloring property of a rare earth stabilizer in the prior art, the invention provides a thienyl rare earth stabilizer for PVC, and the molecular structure of the rare earth stabilizer simultaneously contains a double-molecule thiophene ring, carboxyl, amide, aliphatic long chain, beta-diketone and lanthanoid structure, so that the rare earth stabilizer has excellent thermal stability and light stability, can inhibit initial decomposition and discoloration of PVC, improves the initial coloring property of the rare earth stabilizer, and solves the problem of poor initial coloring property of the rare earth stabilizer in the prior art.
The technical scheme adopted for solving the technical problems is as follows:
a thienyl rare earth stabilizer for PVC has the following structural formula:
wherein R is 1 Is C 17 H 35 Or C 18 H 37 ，R 2 Is C 4 H 9 、C 10 H 21 、C 12 H 25 、C 14 H 29 Or C 16 H 33 。
Another object of the present invention is to provide a method for preparing the thienyl rare earth stabilizer for PVC as described above, comprising the steps of:
s1: dissolving 3, 4-diaminothiophene in DMSO, and placing the solution in a three-neck flask to obtain a first solution;
s2: dissolving 1- (3-bromophenyl) -1, 3-octanedione in DMSO and placing in a constant pressure dropping funnel to obtain a second solution;
s3: dropwise adding the second solution into the first solution, heating to 75-85 ℃, stirring for 2-4h, cooling, standing, and distilling under reduced pressure to obtain an intermediate product I;
s4: adding the intermediate product I, fatty acid, a catalyst, DCC and NHS into DMF, ice-bathing for 1h, stirring at room temperature for 10-20h, filtering, and drying in vacuum to obtain an intermediate product II;
s5: dissolving the intermediate product II and the brominated fatty acid in DMSO, placing in a three-neck flask, heating to 75-85 ℃, stirring for 3-4h, cooling, and standing; adding water, stirring for 30min, standing for layering, drying the organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain an intermediate product III;
s6: adding the intermediate product III and absolute ethyl alcohol into a three-mouth bottle, placing the three-mouth bottle into a constant temperature tank, heating to 60-80 ℃, then adding lanthanide series substances, fully and uniformly stirring, dropwise adding alkaline solution into the three-mouth bottle by using a dropping funnel, adjusting the pH to 6-7, stirring at constant temperature for 4-5.5h, standing, cooling to room temperature, carrying out suction filtration by using a vacuum pump, washing by using deionized water, placing the obtained product into a constant temperature drying oven, and drying at the temperature of 75 ℃ to obtain the thienyl rare earth stabilizer for PVC.
Alternatively, the fatty acid is stearic acid or nonadecanoic acid.
Optionally, the catalyst is acetic acid or p-toluenesulfonic acid.
Alternatively, the brominated fatty acid is 2-bromo-3-methylpentanoic acid, 2-bromolauric acid, 2-bromotetradecanoic acid, 2-bromohexadecanoic acid, or 2-bromostearic acid.
Optionally, the lanthanide is lanthanum chloride.
Optionally, the alkaline solution is a potassium hydroxide solution or an ammonia solution.
Optionally, the molar ratio of the 3, 4-diaminothiophene to the 1- (3-bromophenyl) -1, 3-octanedione is 1:1.
Alternatively, the molar ratio of intermediate I, fatty acid, DCC and NHS in step S4 is 1: (1-1.2): 1:0.5.
Alternatively, the molar ratio of intermediate II to brominated fatty acid in step S5 is 1: (1-1.2); the molar ratio of intermediate III to lanthanide in step S6 is 1: (0.6-0.7).
The beneficial effects of the invention are as follows:
according to the thienyl rare earth stabilizer for PVC, through the synergistic effect of the bimolecular thiophene ring, carboxyl, amide, long aliphatic chain, beta-diketone and lanthanum in the molecular structure, the thienyl rare earth stabilizer has the functions of heat stabilizer in the whole degradation process from initial dechlorination free radical of PVC and formation of double bond from HCl to middle and later stages, and has high-efficiency heat stability; and has the characteristics of initial coloring resistance, light stability, plasticization and lubricity; meanwhile, the material is nontoxic, environment-friendly and transparent, and is beneficial to improving the mechanical properties of the product.
Detailed Description
The present invention will now be described in further detail. The embodiments described below are exemplary and intended to illustrate the invention and should not be construed as limiting the invention, as all other embodiments, based on which a person of ordinary skill in the art would obtain without inventive faculty, are within the scope of the invention.
In the description of the present invention, it should be understood that the terms "first" and "second" are used merely to simplify the description and are not to be construed as indicating or implying relative importance or as implying a number of technical features which are indicated. Thus, a feature defined as "first", "second" may include one or more such feature, either explicitly or implicitly. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
In order to solve the problem of poor initial colorability of a rare earth stabilizer in the prior art, the invention provides a thienyl rare earth stabilizer for PVC, and the structural formula of the rare earth stabilizer is shown as follows:
wherein R is 1 Is C 17 H 35 Or C 18 H 37 ，R 2 Is C 4 H 9 、C 10 H 21 、C 12 H 25 、C 14 H 29 Or C 16 H 33 。
The thienyl rare earth stabilizer for PVC provided by the invention has a molecular structure which simultaneously contains a bimolecular thiophene ring, carboxyl, amide, long aliphatic chain, beta-diketone and lanthanoid structure; wherein, rare earth lanthanum provides an empty orbit to capture chloride ions and HCl; o, N in the ester group amide can form coordination bond with rare earth lanthanum and can adsorb HCl; the active methylene structure in the beta-diketone can capture free radicals generated by PVC decomposition and inhibit discoloration caused by the decomposition in the early stage; C-S bond in thiophene ring can be broken to form active free radical to catch free radical generated by PVC decomposition; the conjugated double bond in the thiophene ring can generate an addition reaction with the double bond formed in the PVC decomposition process, so that the degradation of a molecular chain can be stopped, the color change can be further inhibited, and the mechanical strength of the PVC can be improved; meanwhile, a plurality of long-fat straight chains and branched structures can be dispersed among PVC molecular chains, so that the intermolecular acting force of PVC is weakened, the plasticizing lubricity is realized, and the processing temperature of PVC is reduced.
In addition, the rare earth lanthanum element in the thienyl rare earth stabilizer for PVC can absorb ultraviolet rays of 230-320mm, improve weather resistance and have light stability.
Therefore, the thienyl rare earth stabilizer for PVC provided by the invention has the advantages that the thienyl rare earth stabilizer has the function of heat stabilizer in the whole degradation process from initial dechlorination free radical of PVC and HCl to middle and later double bond formation through the synergistic effect of bimolecular thiophene ring, carboxyl, amide, aliphatic long chain, beta-diketone and lanthanum in the molecular structure, and has high-efficiency heat stability; and has the characteristics of initial coloring resistance, light stability, plasticization and lubricity; meanwhile, the material is nontoxic, environment-friendly and transparent, and is beneficial to improving the mechanical properties of the product.
Another object of the present invention is to provide a method for preparing the thienyl rare earth stabilizer for PVC as described above, comprising the steps of:
s1: dissolving 3, 4-diaminothiophene in dimethyl sulfoxide (DMSO), and placing in a three-neck flask to obtain a first solution;
s2: dissolving 1- (3-bromophenyl) -1, 3-octanedione in DMSO and placing in a constant pressure dropping funnel to obtain a second solution;
s3: slowly dripping the second solution into the first solution, heating to 75-85 ℃, stirring for 2-4h, cooling, standing, and distilling under reduced pressure to obtain an intermediate product I;
s4: adding the intermediate product I, fatty acid, a catalyst, dicyclohexylcarbodiimide (DCC) and N-hydroxysuccinimide (NHS) into N, N-Dimethylformamide (DMF), ice-bathing for 1h, stirring at room temperature for 10-20h, filtering, and drying in vacuum to obtain an intermediate product II;
s5: dissolving intermediate II and bromofatty acid in DMSO, placing in a three-neck flask, heating to 75-85deg.C, stirring for 3-4 hr, cooling, and standing; adding water, stirring for 30min, standing for layering, drying the organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain an intermediate product III;
s6: adding the intermediate product III and absolute ethyl alcohol into a three-mouth bottle, placing the three-mouth bottle into a constant temperature tank, heating to 60-80 ℃, then adding lanthanide series substances, fully and uniformly stirring, dropwise adding alkaline solution into the three-mouth bottle by using a dropping funnel, adjusting the pH value to 6-7, stirring the three-mouth bottle at constant temperature for 4-5.5h, standing, cooling to room temperature, carrying out suction filtration by using a vacuum pump, washing the three-mouth bottle by using deionized water, placing the obtained product into a constant temperature drying box, setting the temperature to 75 ℃, and drying to obtain a target product IV, namely the thienyl rare earth stabilizer for PVC.
The invention takes 3, 4-diamino thiophene, 1- (3-bromophenyl) -1, 3-octadione, fatty acid, brominated fatty acid and lanthanide series substances as raw materials, and the thienyl rare earth stabilizer for PVC is obtained through multi-step reactions such as substitution, amidation and the like; the novel thienyl rare earth stabilizer for PVC not only effectively solves the problems of unsatisfactory thermal stability and poor initial coloring resistance of the conventional PVC rare earth stabilizer, but also has the performances of light stability, lubrication and the like while having high-efficiency thermal stability, and the material can be widely applied to various PVC products.
Further, the preferred fatty acid of the present invention is stearic acid or nonadecanoic acid; preferably the catalyst is acetic acid or p-toluene sulfonic acid; preferably the brominated fatty acid is 2-bromo-3-methylpentanoic acid, 2-bromolauric acid, 2-bromotetradecanoic acid, 2-bromohexadecanoic acid or 2-bromostearic acid; preferably the lanthanide is lanthanum chloride; preferably, the alkaline solution is a potassium hydroxide solution or an aqueous ammonia solution, and further preferably, the aqueous ammonia solution is a dilute aqueous ammonia solution.
The alkaline solution is used for regulating the pH value; the concentration and the amount of the alkaline solution can be determined according to the adjustment requirements.
In order to achieve both the reaction rate and the conversion, the molar ratio of 3, 4-diaminothiophene to 1- (3-bromophenyl) -1, 3-octanedione in the present invention is preferably 1:1, and further preferably the molar ratio of 3, 4-diaminothiophene to DMSO in step S1 is 1:40, and the molar ratio of 1- (3-bromophenyl) -1, 3-octanedione to DMSO in step S2 is 1:20.
Preferably, in step S4, the molar ratio of intermediate I, fatty acid, DCC and NHS is 1: (1-1.2): 1:0.5; it is further preferred that the molar ratio of intermediate I to DMF in step S4 is 1:50; and the mass of the catalyst in the step is 0.5% -2% of the mass of the intermediate product I.
The preferred molar ratio of intermediate II to brominated fatty acid in step S5 of the present invention is 1: (1-1.2); preferably, the molar ratio of the intermediate II to DMSO in the step S5 is 1:50; the molar ratio of intermediate III to lanthanide in step S6 is 1: (0.6-0.7); preferably, the molar ratio of intermediate III to absolute ethanol in step S6 is 1:30.
The preparation process of the thienyl rare earth stabilizer for PVC provided by the invention comprises the following steps:
the thienyl rare earth stabilizer for PVC, which has high-efficiency thermal stability and excellent comprehensive performance, is prepared by modifying rare earth elements.
In order that the above-recited objects, features and advantages of the present invention will become more readily apparent, a more particular description of embodiments of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
Example 1
The embodiment provides a preparation method of a thienyl rare earth stabilizer for PVC, which comprises the following steps:
s1: 1mol of 3, 4-diaminothiophene is dissolved in 40mol of DMSO and placed in a three-neck flask to obtain a first solution;
s2: 1mol of 1- (3-bromophenyl) -1, 3-octanedione was dissolved in 20mol of DMSO and placed in a constant pressure dropping funnel to obtain a second solution;
s3: slowly dripping the second solution into the first solution, heating to 75 ℃, stirring for 4 hours, cooling, standing, and distilling under reduced pressure to obtain an intermediate product I;
s4: adding 1mol of intermediate I, 1.2mol of fatty acid, p-toluenesulfonic acid with the mass of 0.5% of that of the intermediate I, 1mol of DCC and 0.5mol of NHS into 50mol of DMF, ice-bathing for 1h, stirring at room temperature for 20h, filtering, and drying in vacuum to obtain an intermediate II;
s5: 1mol of intermediate II and 1.1mol of 2-bromostearic acid are dissolved in 50mol of DMSO, and the mixture is placed in a three-neck flask, heated to 80 ℃, stirred for 4 hours, cooled and stood; slowly adding 60mol of water, stirring for 30min, standing for layering, drying the organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain an intermediate product III;
s6: adding 1mol of intermediate product III and 30mol of absolute ethyl alcohol into a three-mouth bottle, placing the three-mouth bottle into a constant temperature tank, heating to 80 ℃, then adding 0.6mol of lanthanum chloride, fully and uniformly stirring, dropwise adding a proper amount of potassium hydroxide solution into the three-mouth bottle by using a dropping funnel, slowly dropwise adding the three-mouth bottle, regulating the pH value to 6, stirring the three-mouth bottle at constant temperature for 4 hours, standing, cooling to room temperature, carrying out suction filtration by using a vacuum pump, washing the three-mouth bottle for 3 times by using deionized water, placing the obtained product into a constant temperature drying box, and drying the obtained product at the temperature of 75 ℃ to obtain a target product IV, namely the thienyl rare earth stabilizer for PVC.
The infrared data are as follows: 3121cm -1 : -NH-present; 1658cm -1 : amide-c=o present; 1715-1742cm -1 : -c=o present; 1618cm -1 : -c=c-present; 3078cm -1 、1430cm -1 、1524cm -1 、767cm -1 : benzene rings (thiophenes) are present; 1485cm -1 、1580cm -1 : amide N-H is present and attenuated; 1354cm -1 : C-N is present; 1382cm -1 、1427cm -1 : the presence of a carboxylate; 793cm -1 : O-La was present.
Example 2
The embodiment provides a preparation method of a thienyl rare earth stabilizer for PVC, which comprises the following steps:
s1: 1mol of 3, 4-diaminothiophene is dissolved in 40mol of DMSO and placed in a three-neck flask to obtain a first solution;
s2: 1mol of 1- (3-bromophenyl) -1, 3-octanedione was dissolved in 20mol of DMSO and placed in a constant pressure dropping funnel to obtain a second solution;
s3: slowly dripping the second solution into the first solution, heating to 85 ℃, stirring for 2 hours, cooling, standing, and distilling under reduced pressure to obtain an intermediate product I;
s4: adding 1mol of intermediate I, 1.2mol of nonadecanoic acid, 1% of p-toluenesulfonic acid by mass of the intermediate I, 1mol of DCC and 0.5mol of NHS into 50mol of DMF, ice-bathing for 1h, stirring for 15h at room temperature, filtering, and drying in vacuum to obtain an intermediate II;
s5: 1mol of intermediate II and 1mol of 2-bromostearic acid are dissolved in 50mol of DMSO, and the mixture is placed in a three-neck flask, heated to 75 ℃, stirred for 3 hours, cooled and stood; slowly adding 60mol of water, stirring for 30min, standing for layering, drying the organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain an intermediate product III;
s6: adding 1mol of intermediate product III and 30mol of absolute ethyl alcohol into a three-mouth bottle, putting the three-mouth bottle into a constant temperature tank, heating to 60 ℃, then adding 0.7mol of lanthanum chloride, fully and uniformly stirring, dropwise adding a proper amount of dilute ammonia water solution by using a dropping funnel, slowly dropwise adding, adjusting the pH value to 7, stirring at constant temperature for 5.5 hours, standing, cooling to room temperature, carrying out suction filtration by using a vacuum pump, washing with deionized water for 3 times, putting the obtained product into a constant temperature drying oven, and drying at the set temperature of 75 ℃ to obtain a target product IV, namely the thienyl rare earth stabilizer for PVC.
The infrared data are as follows: 3115cm -1 : -NH-present; 1652cm -1 : amide-c=o present; 1715-1742cm -1 : -c=o present; 1615cm -1 : -c=c-present; 3076cm -1 、1428cm -1 、1523cm -1 、766cm -1 : benzene rings (thiophenes) are present; 1482cm -1 、1575cm -1 : amide N-H is present and attenuated; 1354cm -1 : C-N is present; 1382cm -1 、1427cm -1 : the presence of a carboxylate; 790cm -1 : O-La was present.
Example 3
The embodiment provides a preparation method of a thienyl rare earth stabilizer for PVC, which comprises the following steps:
s1: 1mol of 3, 4-diaminothiophene is dissolved in 40mol of DMSO and placed in a three-neck flask to obtain a first solution;
s2: 1mol of 1- (3-bromophenyl) -1, 3-octanedione was dissolved in 20mol of DMSO and placed in a constant pressure dropping funnel to obtain a second solution;
s3: slowly dripping the second solution into the first solution, heating to 80 ℃, stirring for 3 hours, cooling, standing, and distilling under reduced pressure to obtain an intermediate product I;
s4: adding 1mol of intermediate I, 1mol of stearic acid, acetic acid with the mass being 2% of that of the intermediate I, 1mol of DCC and 0.5mol of NHS into 50mol of DMF, ice-bathing for 1h, stirring for 15h at room temperature, filtering, and drying in vacuum to obtain an intermediate II;
s5: 1mol of intermediate II and 1.2mol of 2-bromotetradecanoic acid are dissolved in 50mol of DMSO, and the mixture is placed in a three-neck flask, heated to 80 ℃, stirred for 3.5h, cooled and stood; slowly adding 60mol of water, stirring for 30min, standing for layering, drying the organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain an intermediate product III;
s6: adding 1mol of intermediate product III and 30mol of absolute ethyl alcohol into a three-mouth bottle, placing the three-mouth bottle into a constant temperature tank, heating to 70 ℃, then adding 0.7mol of lanthanum chloride, fully and uniformly stirring, dropwise adding a proper amount of potassium hydroxide solution into the three-mouth bottle by using a dropping funnel, slowly dropwise adding the three-mouth bottle, regulating the pH value to 7, stirring the three-mouth bottle at constant temperature for 5 hours, standing, cooling to room temperature, carrying out suction filtration by using a vacuum pump, washing the three-mouth bottle for 3 times by using deionized water, placing the obtained product into a constant temperature drying box, and drying the obtained product at the temperature of 75 ℃ to obtain a target product IV, namely the thienyl rare earth stabilizer for PVC.
The infrared data are as follows: 3120cm -1 : -NH-present; 1658cm -1 : amide-c=o present; 1715-1742cm -1 : -c=o present; 1619cm -1 : -c=c-present; 3077cm -1 、1430cm -1 、1523cm -1 、767cm -1 : benzene rings (thiophenes) are present; 1485cm -1 、1580cm -1 : amide N-H is present and attenuated; 1354cm -1 : C-N is present; 1382cm -1 、1427cm -1 : the presence of a carboxylate; 792cm -1 : O-La was present.
Example 4
The embodiment provides a preparation method of a thienyl rare earth stabilizer for PVC, which comprises the following steps:
s1: 1mol of 3, 4-diaminothiophene is dissolved in 40mol of DMSO and placed in a three-neck flask to obtain a first solution;
s2: 1mol of 1- (3-bromophenyl) -1, 3-octanedione was dissolved in 20mol of DMSO and placed in a constant pressure dropping funnel to obtain a second solution;
s3: slowly dripping the second solution into the first solution, heating to 80 ℃, stirring for 4 hours, cooling, standing, and distilling under reduced pressure to obtain an intermediate product I;
s4: adding 1mol of intermediate I, 1.1mol of nonadecanoic acid, p-toluenesulfonic acid with the mass being 2% of that of the intermediate I, 1mol of DCC and 0.5mol of NHS into 50mol of DMF, ice-bathing for 1h, stirring for 10h at room temperature, filtering, and drying in vacuum to obtain an intermediate II;
s5: 1mol of intermediate II and 1.1mol of 2-bromolauric acid are dissolved in 50mol of DMSO, and the mixture is placed in a three-neck flask, heated to 80 ℃, stirred for 4 hours, cooled and stood; slowly adding 60mol of water, stirring for 30min, standing for layering, drying the organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain an intermediate product III;
s6: adding 1mol of intermediate product III and 30mol of absolute ethyl alcohol into a three-mouth bottle, putting the three-mouth bottle into a constant temperature tank, heating to 70 ℃, then adding 0.7mol of lanthanum chloride, fully and uniformly stirring, dropwise adding a proper amount of dilute ammonia water solution by using a dropping funnel, slowly dropwise adding, adjusting the pH value to 7, stirring at constant temperature for 4.5 hours, standing, cooling to room temperature, carrying out suction filtration by using a vacuum pump, washing with deionized water for 3 times, putting the obtained product into a constant temperature drying oven, and drying at the set temperature of 75 ℃ to obtain a target product IV, namely the thienyl rare earth stabilizer for PVC.
The infrared data are as follows: 3122cm -1 : -NH-present; 1658cm -1 : amide-c=o present; 1715-1742cm -1 : -c=o present; 1616cm -1 : -c=c-present; 3079cm -1 、1430cm -1 、1524cm -1 、767cm -1 : benzene rings (thiophenes) are present; 1485cm -1 、1580cm -1 : amide N-H is present and attenuated; 1354cm -1 : C-N is present; 1382cm -1 、1427cm -1 : the presence of a carboxylate; 793cm -1 : O-La was present.
Example 5
The embodiment provides a preparation method of a thienyl rare earth stabilizer for PVC, which comprises the following steps:
s1: 1mol of 3, 4-diaminothiophene is dissolved in 40mol of DMSO and placed in a three-neck flask to obtain a first solution;
s2: 1mol of 1- (3-bromophenyl) -1, 3-octanedione was dissolved in 20mol of DMSO and placed in a constant pressure dropping funnel to obtain a second solution;
s3: slowly dripping the second solution into the first solution, heating to 85 ℃, stirring for 3 hours, cooling, standing, and distilling under reduced pressure to obtain an intermediate product I;
s4: adding 1mol of intermediate I, 1.1mol of stearic acid, acetic acid with the mass being 1.5% of that of the intermediate I, 1mol of DCC and 0.5mol of NHS into 50mol of DMF, ice-bathing for 1h, stirring at room temperature for 18h, filtering, and drying in vacuum to obtain an intermediate II;
s5: 1mol of intermediate II and 1.2mol of 2-bromohexadecanoic acid are dissolved in 50mol of DMSO, and the mixture is placed in a three-neck flask, heated to 85 ℃, stirred for 4 hours, cooled and stood; slowly adding 60mol of water, stirring for 30min, standing for layering, drying the organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain an intermediate product III;
s6: adding 1mol of intermediate product III and 30mol of absolute ethyl alcohol into a three-mouth bottle, putting the three-mouth bottle into a constant temperature tank, heating to 80 ℃, then adding 0.7mol of lanthanum chloride, fully and uniformly stirring, dropwise adding a proper amount of dilute ammonia water solution by using a dropping funnel, slowly dropwise adding, adjusting the pH value to 6, stirring at constant temperature for 5 hours, standing, cooling to room temperature, carrying out suction filtration by using a vacuum pump, washing with deionized water for 3 times, putting the obtained product into a constant temperature drying oven, and drying at the temperature of 75 ℃ to obtain a target product IV, namely the thienyl rare earth stabilizer for PVC.
The infrared data are as follows: 3122cm -1 : -NH-present; 1660cm -1 : amide-c=o present; 1715-1742cm -1 : -c=o present; 1619cm -1 : -c=c-present; 3078cm -1 、1430cm -1 、1524cm -1 、767cm -1 : benzene rings (thiophenes) are present; 1485cm -1 、1580cm -1 : amide N-H is present and attenuated; 1355cm -1 : C-N is present; 1382cm -1 、1427cm -1 : the presence of a carboxylate; 793cm -1 : O-La was present.
The thienyl rare-earth stabilizer for PVC obtained in example 1 was used as a base material for application example, and a PVC sample was prepared.
Application example 1
The application embodiment provides a PVC sheet, which is prepared from the following raw materials in parts by weight:
the preparation method of the PVC sheet comprises the following steps:
mixing the above materials, plasticating at 170deg.C for 15min, and tabletting with a flat vulcanizing machine.
Application example 2
The application embodiment provides a PVC sheet, which is prepared from the following raw materials in parts by weight:
the preparation method of the PVC sheet comprises the following steps:
mixing the above materials, plasticating at 170deg.C for 15min, and tabletting with a flat vulcanizing machine.
Application example 3
The application embodiment provides a PVC sheet, which is prepared from the following raw materials in parts by weight:
the preparation method of the PVC sheet comprises the following steps:
mixing the above materials, plasticating at 170deg.C for 20min, and tabletting with a flat vulcanizing machine.
Application example 4
The application embodiment provides a PVC sheet, which is prepared from the following raw materials in parts by weight:
the preparation method of the PVC sheet comprises the following steps:
mixing the above materials, plasticating at 170deg.C for 25min, and tabletting with a flat vulcanizing machine.
The PVC sheets of application comparative examples 1 to 4 were all compared with application example 1:
comparative example 1 was used
The application comparative example provides a PVC sheet, which consists of the following raw materials in parts by weight:
the preparation method of the PVC sheet comprises the following steps:
mixing the above materials, plasticating at 170deg.C for 15min, and tabletting with a flat vulcanizing machine.
Comparative example 2 was used
The application comparative example provides a PVC sheet, which consists of the following raw materials in parts by weight:
the preparation method of the PVC sheet comprises the following steps:
mixing the above materials, plasticating at 170deg.C for 15min, and tabletting with a flat vulcanizing machine.
Comparative example 3 was used
The application comparative example provides a PVC sheet, which consists of the following raw materials in parts by weight:
the preparation method of the PVC sheet comprises the following steps:
mixing the above materials, plasticating at 170deg.C for 15min, and tabletting with a flat vulcanizing machine.
Comparative example 4 was used
The application comparative example provides a PVC sheet, which consists of the following raw materials in parts by weight:
the preparation method of the PVC sheet comprises the following steps:
mixing the above materials, plasticating at 170deg.C for 15min, and tabletting with a flat vulcanizing machine.
The physical properties, including mechanical properties and thermal stability, of the PVC sheets prepared in application examples 1 to 4 and application comparative examples 1 to 4 of the present invention were measured respectively, and the test methods were as follows:
(1) Plasticizing time: the thermal stability of the PVC samples was tested using a torque rheometer. The preheating temperature of the mixing chamber is 180 ℃ and the rotating speed is 35r/min.
(2) Static thermal stability: congo red method, see GB/T2917.1-2002.
(3) Apparent color: the final color of the coupon after removal from the roll was visually observed. Apparent color representation method: 5 is the lightest color, namely the optimal color; 1 is the darkest, i.e. worst, color.
(4) Light stabilization effect: and (3) pyrolyzing PVC in an oil bath at a constant temperature of 200 ℃, dissolving the pyrolyzed PVC in THF, measuring an ultraviolet-visible spectrum, and setting the wavelength to be in the range of 200-500 nm. The light stabilization effect is expressed by the following steps: 5 is the lowest molar absorption coefficient, namely the optimal light stabilization effect; 1 is the maximum molar absorption coefficient, i.e. the worst light stabilization effect.
(5) Mechanical property test: a strong extensometer is used. In the test, the clamping distance of the sample is 20mm, the stretching speed is 10mm/min, and the test temperature is room temperature. Each group of samples was tested 30 times and the results averaged.
The test results are shown in table 1 below:
TABLE 1
As shown in the data in the table, compared with the conventional PVC heat stabilizer calcium zinc stabilizer and the conventional organotin stabilizer, the thienyl rare earth stabilizer for PVC has obvious advantages in static and dynamic heat stability, has a good light stabilization effect, and has obviously improved mechanical properties; compared with the conventional rare earth stabilizer, the thienyl rare earth stabilizer for PVC has obvious advantages in plasticizing time, heat stability, light stability and mechanical property. Wherein, the color is obviously better than that of a single rare earth stabilizer and a compound rare earth stabilizer in apparent color (initial coloring resistance).
In conclusion, compared with the existing heat stabilizer, particularly the existing rare earth stabilizer, the thienyl rare earth stabilizer for PVC not only solves the problems of unsatisfactory stabilizing effect and poor initial coloring resistance, but also has better light stabilizing effect, can improve the mechanical property of PVC materials, is nontoxic, environment-friendly and transparent, is flexible to use, and can be widely applied to various PVC products.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (10)
1. A thienyl rare earth stabilizer for PVC is characterized by having the following structural formula:
wherein R is 1 Is C 17 H 35 Or C 18 H 37 ，R 2 Is C 4 H 9 、C 10 H 21 、C 12 H 25 、C 14 H 29 Or C 16 H 33 。
2. A method for preparing the thienyl rare-earth stabilizer for PVC according to claim 1, comprising the steps of:
s1: dissolving 3, 4-diaminothiophene in DMSO, and placing the solution in a three-neck flask to obtain a first solution;
s2: dissolving 1- (3-bromophenyl) -1, 3-octanedione in DMSO and placing in a constant pressure dropping funnel to obtain a second solution;
s3: dropwise adding the second solution into the first solution, heating to 75-85 ℃, stirring for 2-4h, cooling, standing, and distilling under reduced pressure to obtain an intermediate product I;
s4: adding the intermediate product I, fatty acid, a catalyst, DCC and NHS into DMF, ice-bathing for 1h, stirring at room temperature for 10-20h, filtering, and drying in vacuum to obtain an intermediate product II;
s5: dissolving the intermediate product II and the brominated fatty acid in DMSO, placing in a three-neck flask, heating to 75-85 ℃, stirring for 3-4h, cooling, and standing; adding water, stirring for 30min, standing for layering, drying the organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain an intermediate product III;
s6: adding the intermediate product III and absolute ethyl alcohol into a three-mouth bottle, placing the three-mouth bottle into a constant temperature tank, heating to 60-80 ℃, then adding lanthanide series substances, fully and uniformly stirring, dropwise adding alkaline solution into the three-mouth bottle by using a dropping funnel, adjusting the pH to 6-7, stirring at constant temperature for 4-5.5h, standing, cooling to room temperature, carrying out suction filtration by using a vacuum pump, washing by using deionized water, placing the obtained product into a constant temperature drying oven, and drying at the temperature of 75 ℃ to obtain the thienyl rare earth stabilizer for PVC.
3. The method for producing a thienyl rare stabilizer for PVC as claimed in claim 2, wherein the fatty acid is stearic acid or nineteen acids.
4. The method for preparing a thienyl rare stabilizer for PVC as recited in claim 2, wherein the catalyst is acetic acid or p-toluene sulfonic acid.
5. The method for producing a thienyl rare stabilizer for PVC according to claim 2, wherein the brominated fatty acid is 2-bromo-3-methylpentanoic acid, 2-bromolauric acid, 2-bromotetradecanoic acid, 2-bromohexadecanoic acid or 2-bromostearic acid.
6. The method for producing a thienyl rare stabilizer for PVC as claimed in claim 2, wherein the lanthanoid is lanthanum chloride.
7. The method for producing a thienyl rare stabilizer for PVC according to claim 2, wherein the alkaline solution is a potassium hydroxide solution or an aqueous ammonia solution.
8. The method for producing a thienyl rare stabilizer for PVC according to any of claims 2 to 7, wherein the molar ratio of 3, 4-diaminothiophene to 1- (3-bromophenyl) -1, 3-octanedione is 1:1.
9. The method for preparing a thienyl rare stabilizer for PVC according to any of claims 2 to 7, wherein the molar ratio of the intermediate I, fatty acid, DCC and NHS in the step S4 is 1: (1-1.2): 1:0.5.
10. The method for preparing a thienyl rare-earth stabilizer for PVC according to any one of claims 2 to 7, wherein the molar ratio of the intermediate II to the brominated fatty acid in the step S5 is 1: (1-1.2); the molar ratio of intermediate III to lanthanide in step S6 is 1: (0.6-0.7).
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