CN109836613A - Organic acid zinc alkanol amine compound and its heat stabilizer purposes - Google Patents
Organic acid zinc alkanol amine compound and its heat stabilizer purposes Download PDFInfo
- Publication number
- CN109836613A CN109836613A CN201910057764.7A CN201910057764A CN109836613A CN 109836613 A CN109836613 A CN 109836613A CN 201910057764 A CN201910057764 A CN 201910057764A CN 109836613 A CN109836613 A CN 109836613A
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- CN
- China
- Prior art keywords
- zinc
- organic acid
- amine compound
- alkanol amine
- acid zinc
- Prior art date
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- Granted
Links
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000011701 zinc Substances 0.000 title claims abstract description 61
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 61
- 150000007524 organic acids Chemical class 0.000 title claims abstract description 46
- -1 amine compound Chemical class 0.000 title claims abstract description 37
- 239000012760 heat stabilizer Substances 0.000 title claims abstract description 10
- 150000003751 zinc Chemical class 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000012736 aqueous medium Substances 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 48
- 239000000460 chlorine Substances 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 11
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 claims description 8
- 239000011746 zinc citrate Substances 0.000 claims description 8
- 235000006076 zinc citrate Nutrition 0.000 claims description 8
- 229940068475 zinc citrate Drugs 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 claims description 6
- CANRESZKMUPMAE-UHFFFAOYSA-L Zinc lactate Chemical compound [Zn+2].CC(O)C([O-])=O.CC(O)C([O-])=O CANRESZKMUPMAE-UHFFFAOYSA-L 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011670 zinc gluconate Substances 0.000 claims description 6
- 235000011478 zinc gluconate Nutrition 0.000 claims description 6
- 229960000306 zinc gluconate Drugs 0.000 claims description 6
- 239000011576 zinc lactate Substances 0.000 claims description 6
- 229940050168 zinc lactate Drugs 0.000 claims description 6
- 235000000193 zinc lactate Nutrition 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- IOAOAKDONABGPZ-UHFFFAOYSA-N 2-amino-2-ethylpropane-1,3-diol Chemical compound CCC(N)(CO)CO IOAOAKDONABGPZ-UHFFFAOYSA-N 0.000 claims description 3
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- XDWXRAYGALQIFG-UHFFFAOYSA-L zinc;propanoate Chemical compound [Zn+2].CCC([O-])=O.CCC([O-])=O XDWXRAYGALQIFG-UHFFFAOYSA-L 0.000 claims description 2
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- WGYFACNYUJGZQO-UHFFFAOYSA-N aminomethanetriol Chemical group NC(O)(O)O WGYFACNYUJGZQO-UHFFFAOYSA-N 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 235000016804 zinc Nutrition 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- 239000003381 stabilizer Substances 0.000 abstract description 19
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 30
- 239000000463 material Substances 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical group OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 14
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 11
- 239000000174 gluconic acid Substances 0.000 description 11
- 235000012208 gluconic acid Nutrition 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 101150035093 AMPD gene Proteins 0.000 description 10
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000004246 zinc acetate Substances 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000004310 lactic acid Substances 0.000 description 4
- 235000014655 lactic acid Nutrition 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 208000030208 low-grade fever Diseases 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012958 reprocessing Methods 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012956 testing procedure Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- 229960000314 zinc acetate Drugs 0.000 description 2
- 235000013904 zinc acetate Nutrition 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- 235000004694 Eucalyptus leucoxylon Nutrition 0.000 description 1
- 244000166102 Eucalyptus leucoxylon Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- BUUANTVIKUHWDL-UHFFFAOYSA-N n-[2-(pyridin-2-yldisulfanyl)ethyl]acetamide Chemical compound CC(=O)NCCSSC1=CC=CC=N1 BUUANTVIKUHWDL-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention discloses a kind of organic acid zinc alkanol amine compound and its heat stabilizer purposes, the ratio that alkanolamine and zinc salts of organic acid are 1-2:1 in molar ratio is reacted in an aqueous medium, to obtain organic acid zinc alkanol amine compound, catalyst can also be added when necessary, reaction process of the invention carries out at a lower temperature, no three wastes discharges in reaction process, the aqueous that product steams water after reaction or simple separation separates can recycle, the advantages of recycling, this embodies organic acid zinc alkanol amine compound preparation process；Reacting product obtained not only has good thermal stability, but also to a certain degree or is fully solved above-mentioned zinc and burns problem, advantageously reduces the cost of existing calcium zinc stabilizer, and widely promoted and applied.
Description
Technical field
The present invention relates to the technical fields of polymeric material containing chlorine, and in particular to a kind of organic acid zinc alkanol amine compound and its heat
Stabilizer purposes.
Background technique
Chlorine-containing polymer, for example, the copolymer of polyvinyl chloride (PVC), vinyl chloride and vinyl acetate and poly- (1,1- bis-
Vinyl chloride) etc., it is commonly used to manufacture many articles such as tubing, window profile, baffle, bottle, covers walling material and packing film.People
Have been carried out it is many by stabilizer being added in chlorine-containing polymer to improve the trial of the color retention of fluoropolymer resin,
Color keep especially in process, such as during initial manufacture and during any subsequent reprocessing.It uses now
Most stabiliser compositions include such as tin, barium, cadmium and even lead metal.Although these stabiliser compositions can effectively subtract
Colour fading during few initial manufacture and any subsequent reprocessing, but environment and it is other due to, exploitation is not contained
Tin, barium, cadmium and/or lead stabilizer interest it is growing.
At home, the exploitation and popularization of calcium zinc heat stabilizer carry out in high gear.Zinc polycarboxylate and calcium carboxylates are used
Combination is used as stabilizer, however most of is used alone or in combination as zinc compound caused by chlorine-containing polymer stabilizer very
Fast degradation or " zinc burning " after short good color.In order to obtain acceptable stability from the combination of zinc-calcium, it is necessary to using being permitted
More additives or co-stabilizer, to increase the cost of stabiliser system.Therefore, there is an urgent need to find a kind of new thermostabilization
Agent.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of organic acid zinc alkanol amine compound and its heat stabilizer is used
On the way, with good thermal stability, and there is certain anti-zinc to burn performance.
Technical solution is as follows: a kind of organic acid zinc alkanol amine compound, and key is to prepare in the following manner: by alkane
Hydramine and zinc salts of organic acid are that the ratio of 1-2:1 is reacted in an aqueous medium in molar ratio, so that it is multiple to obtain organic acid zinc alkanolamine
Object is closed, the general structure of the alkanolamine is as follows:
Wherein R is methyl, ethyl or methylol.
Reaction product obtained by adopting the above technical scheme can remove water by vacuum distillation, and/or by simply dividing
From water is removed, can be used directly as stabilizer without purifying, therefore be called " compound ", simultaneous reactions object alkanolamine
It is also possible to two or more, the product obtained in this way may not be single substance, and thus obtained " compound " has good
Thermal stability, and there is good anti-zinc to burn performance.
As a further preference:
Above-mentioned reaction carries out at 70-80 DEG C, pH≤7 of reaction system.
Catalyst can also be added in the reaction system, the catalyst is sulfuric acid, nitric acid, hydrochloric acid or acetic acid, the catalysis
Agent dosage is the 0.1-2% of the organic acid zinc salt quality.The catalyst of addition can be 0.1%, 0.3%, 0.5%, 1% or
Person 2% etc..
Above-mentioned zinc salts of organic acid is zinc acetate, zinc propionate, zinc lactate, zinc benzoate, 6- acetylamino sour zinc, glucose
Sour zinc or zinc citrate.
Above-mentioned alkanolamine is 2- amino-2-methyl -1,3- propylene glycol, 2- amino -2- ethyl -1,3- propylene glycol or three hydroxyls
Vlmethyl methane.
Above-mentioned alkanolamine is trishydroxymethylaminomethane.
A kind of heat stabilizer purposes of organic acid zinc alkanol amine compound, key are: processed in chlorine-containing polymer
The organic acid zinc alkanol amine compound of above-mentioned preparation is added in journey as heat stabilizer.It joined organic acid prepared by the present invention
There is chlorine-containing polymer better thermal stability and anti-zinc to burn performance after zinc alkanol amine compound.
A kind of preparation method of organic acid zinc alkanol amine compound, key are to prepare by above-mentioned preparation method, and
The temperature for controlling reaction system is 70-80 DEG C, pH≤7, to obtain the organic acid zinc alkanol amine compound.
The utility model has the advantages that reaction process of the invention carries out at a lower temperature, no three wastes discharges in reaction process, after reaction
The aqueous that product steams water or simple separation separates can recycle, and be recycled, this embodies organic acid zinc alkanol amine compound
The advantages of preparation process；Reacting product obtained not only has good thermal stability, but also to a certain degree or is fully solved above-mentioned
Existing zinc burns problem, advantageously reduces the cost of existing calcium zinc stabilizer, and widely promoted and applied.
Specific embodiment
Below with reference to embodiment, the invention will be further described.
One, the preparation of organic acid zinc alkanol amine compound
It is as follows to can be used for present invention implementation alkanolamine general formula structure:
(referred to as including 2- amino-2-methyl -1,3- propylene glycol (abbreviation AMPD), 2- amino -2- ethyl -1,3- propylene glycol
AEPD), trishydroxymethylaminomethane (abbreviation THAM), these compounds are commercially available, and it is real that customary commercial grade is suitable for the present invention
It applies.It can also be routinely condensed by nitroparaffins and aldehydes, then reduction treatment is made by oneself.
(I) used in the present invention all has good solubility: trishydroxymethylaminomethane powder in water and ethyl alcohol,
At 25 DEG C, solubility is 500g/L in water, and solubility is 22g/L in 95% ethyl alcohol；2- amino-2-methyl -1,3- propylene glycol
Crystalline powder, at 20 DEG C, solubility is 2500g/L in water, is dissolved in ethyl alcohol；2- amino -2- ethyl -1,3- propylene glycol is pale yellow
Color viscous liquid is soluble easily in water, is dissolved in ethyl alcohol.
(I) of the invention is dissolved in water and ethyl alcohol all in alkalinity: the THAM aqueous solution of 0.1mol, pH value 10.4；
The AMPD aqueous solution of 0.1mol, pH value 10.8；The AEPD aqueous solution of 0.1mol, pH value 10.8.Good dissolubility is conducive to
Reaction progress and dissolved alkaline reaction control and endpoint.
Ingredient of the carboxylate of known zinc as calcium zinc stabilizer, thermostabilization chlorine-containing polymer and prevent its thermal degradation.It is real
The carboxylate for being proved most of zinc alone or in combination is trampled used as zinc compound caused by chlorine-containing polymer stabilizer very
Fast degradation or " burning " or enough stability cannot be shown to chlorine-containing polymer after short good color.The present invention uses
Zinc salts of organic acid in, it is water-soluble to have: zinc acetate (at 20 DEG C, be 30g/100, also be soluble in alcohol), zinc lactate (it is soluble easily in water,
Be slightly soluble in ethyl alcohol), zinc benzoate (acicular crystal can be dissolved in water and ethyl alcohol), 6- acetylamino sour zinc (be soluble in boiling water,
Slightly soluble in cold water), zinc gluconate (in the hot water dissolve)；Be slightly soluble in water has: zinc citrate etc..These compounds can quotient
Purchase, customary commercial grade are suitable for the present invention and implement, and zinc salts of organic acid used in the present invention is not limited to above-mentioned several certainly, also
Be dissolved in hot water or cold water including other or be slightly soluble in water and boiling point and decomposition temperature be greater than chlorine-containing polymer processing temperature its
His zinc salts of organic acid, the temperature are usually no more than 250 DEG C, these zinc salts of organic acid react obtained compound with alkanolamine
Basic performance and aforementioned several zinc salts of organic acid product property difference it is little.
Embodiment 1, acetic acid (THAM)2Zinc complexes (1) preparation:
Trishydroxymethylaminomethane is provided by Suzhou subfamily Science and Technology Co., Ltd. and Shandong Ying Lang Chemical Co., Ltd.；
Remaining raw material is commercially available, the pure grade of chemistry.Reaction raw materials quality g is 100% content.
Under stiring, it will be dissolved in 30ml distilled water under 12.0g (0.1mol) THAM room temperature or low-grade fever, it is transparent pale yellow
Color solution is fitted into dropping funel stand-by；
In three mouthfuls of neck round-bottom flasks of 250ml, will 9.2g (0.05mol) zinc acetate stirring it is lower dissolve by heating in
It is in colourless transparent solution in 120ml water.75 DEG C are warming up to, the THAM aqueous solution of aforementioned preparation is added dropwise, temperature is protected during dropwise addition
It holds at 70~80 DEG C, pH keeps≤7；It is added dropwise (about 30min), cools to 50 DEG C after being kept for 2 hours, vacuumize removing water
Point, obtain transparent colloid i.e. acetic acid (THAM)2Zinc complexes (1).
Embodiment 2, acetic acid (THAM) zinc complexes (2) preparation:
It is operated by example 1, but 0.1mol zinc acetate substitutes 0.05mol zinc acetate, obtains the wet shape solid i.e. second of white
Sour (THAM) zinc complexes (2).
Embodiment 3, gluconic acid (THAM)2Zinc complexes (3) preparation:
It is operated by example 1, but the zinc acetate of the zinc gluconate of 22.8g (0.05mol) substitution 9.2g (0.05mol),
Obtain pale yellow gum i.e. gluconic acid (THAM)2Zinc complexes (3).
Embodiment 4, gluconic acid (THAM) zinc complexes (4) preparation:
It is operated by example 1, but 0.05mol THAM substitutes 0.1mol THAM, obtains yellowish colloid i.e. gluconic acid
(THAM) zinc complexes (4).
Embodiment 5, citric acid (THAM)2Zinc complexes (5) preparation:
Under stiring, it is dissolved in 30ml distilled water under 12.0g (0.1mol) THAM room temperature or low-grade fever, it is transparent light yellow
Solution is fitted into dropping funel stand-by；
In three mouthfuls of neck round-bottom flasks of 250ml, the zinc citrate of 28.8g (0.05mol) is added and as catalyst
0.14g nitric acid (0.5% zinc citrate quality) heats to 70 DEG C in 120ml water under stirring, be acidified 2hr；It is added dropwise aforementioned
The THAM aqueous solution of preparation, temperature is maintained at 70~80 DEG C during dropwise addition, and PH keeps≤7；It is added dropwise (about 3hr), keeps 2
Hour or more after cool to 50 DEG C, vacuumize removing moisture, obtain white solid citric acid (THAM)2Zinc complexes (5).
Catalyst nitric acid in above-mentioned preparation process may be replaced by sulfuric acid, hydrochloric acid or acetic acid etc., the catalyst of addition
It can be any number between the 0.1-2% of organic acid zinc salt quality, do not influence being normally carried out for reaction.
Embodiment 6, citric acid (THAM) zinc complexes (6) preparation:
It is operated by example 5, but 0.05mol THAM substitutes 0.1mol THAM, obtains white solid citric acid (THAM)
Zinc complexes (6).
Other embodiments prepare acetic acid (AEPD) referring to the operation of example 1 and relevant parameter2Zinc complexes, lactic acid (AEPD)2
Zinc complexes, gluconic acid (AEPD)2Zinc complexes, acetic acid (AMPD)2Zinc complexes and citric acid (AEPD)2Zinc complexes；
Referring to the operation of embodiment 2 and relevant parameter, acetic acid (AEPD) zinc complexes, lactic acid (AEPD) zinc complexes, gluconic acid are prepared
(AEPD) zinc complexes, acetic acid (AMPD) zinc complexes, gluconic acid (AEPD) zinc complexes and citric acid (AEPD) zinc are multiple
Close object.
Two, thermal stability experiment and anti-zinc burn experiment
(1) thermal stability is tested, and used experimental material, equipment are as follows:
Rheometer: model XSS-300 torque rheometer, the manufacture of Shanghai Kechuang rubber and plastics machine equipment Co., Ltd；Parameter: turn
Square 35rpm, 180 DEG C of temperature, time 5min.
Test equipment: model NS800 colour photometer, the manufacture of 3NH Technology Co., Ltd..
Organic acid zinc alkanolamine prepared by the embodiment of the present invention is added as stabilization in base material formulation such as table 1 in base-material
Agent prepares mixture and is tested, separately take base-material be separately added into THAM, AEPD, AMPD, zinc acetate, zinc lactate, zinc gluconate,
Zinc citrate prepares mixture as stabilizer and compares, prescription of mixed materials as indicated with 2:
1 base material formulation of table
| Name of material | Measure (by weight) |
| PVC-SG5 (K value) | 100 parts |
| CaCO3 | 20 parts |
| Rutile titanium white powder | 1.5 part |
| CPE 135 | 4.5 part |
2 prescription of mixed materials of table
| Name of material | Weight (g) |
| Base-material | 68 |
| Lubricant (PE wax) | 1 |
| Stabilizer | 1 |
| It amounts to | 70 |
Testing procedure: it is uniform by prescription of mixed materials mixed material, stablize in rheometer in 180 DEG C, torque 35rpm, adds
Enter mixture, rheology 5min takes out sample, and pressing obtains sample to be tested piece.
It tests judgment method: three times with colour photometer test sample piece, obtaining the average b value of each sample strip.B value is bigger,
Thermal stability is poorer；B value is smaller, and thermal stability is better, and test result is as shown in table 3:
3 heat stability testing result of table
| Serial number | The stabilizer being added in sample strip | Counter sample piece b value |
| 1 | THAM | 9.79 |
| 2 | AEPD | 19.76 |
| 3 | AMPD | 19.87 |
| 4 | Zinc acetate | 15.10 |
| 5 | Acetic acid (THAM) zinc complexes | 10.70 |
| 6 | Acetic acid (THAM)2Zinc complexes | 9.07 |
| 7 | Acetic acid (AEPD) zinc complexes | 12.21 |
| 8 | Acetic acid (AEPD)2Zinc complexes | 10.90 |
| 9 | Acetic acid (AMPD) zinc complexes | 12.58 |
| 10 | Acetic acid (AMPD)2Zinc complexes | 11.13 |
| 11 | Zinc lactate | 15.85 |
| 12 | Lactic acid (AEPD) zinc complexes | 11.62 |
| 13 | Lactic acid (AEPD)2Zinc complexes | 13.23 |
| 14 | Zinc gluconate | 20.26 |
| 15 | Gluconic acid (THAM) zinc complexes | 15.06 |
| 16 | Gluconic acid (THAM)2Zinc complexes | 13.31 |
Table 3 is continuous:
| Serial number | The stabilizer being added in sample strip | Counter sample piece b value |
| 17 | Gluconic acid (AEPD) zinc complexes | 15.28 |
| 18 | Gluconic acid (AEPD)2Zinc complexes | 13.79 |
| 19 | Zinc citrate | 18.58 |
| 20 | Citric acid (THAM) zinc complexes | 13.20 |
| 21 | Citric acid (THAM)2Zinc complexes | 9.34 |
| 22 | Citric acid (AEPD) zinc complexes | 14.36 |
| 23 | Citric acid (AEPD)2Zinc complexes | 11.55 |
From the point of view of test result, the raw materials such as AMPD, AEPD, THAM, zinc acetate, zinc lactate, zinc gluconate, zinc citrate
There is certain thermal stability；Thermal stability > AEPD thermal stability > AMPD thermal stability of THAM in raw material；Product is organic
The thermal stability of sour zinc alkanol amine compound is better than reaction raw materials and with the increase of alkanolamine in raw material, product organic acid
The thermal stability of zinc alkanol amine compound increases；In product organic acid zinc alkanol amine compound, with THAM, AEPD ratio in raw material
The increase of example, the better heat stability of product organic acid zinc alkanol amine compound；From the point of view of the thermal stability of product, reaction raw materials
It is preferred that THAM.
(2) anti-zinc burns experiment, and due to THAM and AMPD, AEPD structure, similar in nature, product is with similitude, this hair
Bright has selected THAM to illustrate that the anti-zinc of product burns performance, the anti-zinc burning property for the product that AMPD, AEPD are reacted with organic acid zinc
Can be similar therewith, it just no longer repeats one by one herein.
Used experimental material, equipment are as follows:
Rheometer: model XSS-300 torque rheometer, the manufacture of Shanghai Kechuang rubber and plastics machine equipment Co., Ltd；Parameter: turn
Square 35rpm, 180 DEG C of temperature, time 3.5min.
Test equipment: model NS800 colour photometer, the manufacture of 3NH Technology Co., Ltd..
Base material formulation such as table 4, is added merely zinc acetylacetonate as stabilizer (comparison) in base-material or this hair is added
The mixture of organic acid zinc alkanolamine and zinc acetylacetonate prepared by bright embodiment prepares mixture, mixture as stabilizer
It is formulated as figure 5 illustrates:
4 base material formulation of table
| Name of material | Measure (by weight) |
| PVC-SG5 (K value) | 100 parts |
| CaCO3 | 20 parts |
| Rutile titanium white powder | 1.5 part |
| CPE 135 | 4.5 part |
5 prescription of mixed materials of table
Testing procedure: it is uniform by prescription of mixed materials mixed material, stablize in rheometer in 180 DEG C, torque 35rpm, adds
Enter mixture, rheology 3.5min takes out sample, and pressing obtains sample to be tested piece.
It tests judgment method: three times with colour photometer test sample piece, obtaining each sample strip average L values.L value is bigger, prevents
Zinc burning property is better；L value is smaller, and anti-zinc burning property is poorer, and test result is as follows shown in table 6:
The anti-zinc of table 6 burns test result
From the point of view of test result, organic acid zinc alkanol amine compound prepared by the present invention has certain anti-zinc burning property, with anti-
The increase in raw material as the alkanolamine ratio of complexing agent is answered, the anti-zinc of product organic acid zinc alkanol amine compound burns performance and increases
Add.
In conclusion organic acid zinc alkanol amine compound prepared by the present invention is used in the processing of chlorine-containing polymer
Afterwards, the thermal stability and anti-zinc burning property of chlorine-containing polymer can effectively be promoted.
Finally, it should be noted that foregoing description is only the preferred embodiment of the present invention, the ordinary skill people of this field
Member under the inspiration of the present invention, without prejudice to the purpose of the present invention and the claims, can make multiple similar tables
Show, such transformation is fallen within the scope of protection of the present invention.
Claims (8)
1. a kind of organic acid zinc alkanol amine compound, it is characterised in that prepare in the following manner: by alkanolamine and organic acid zinc
Salt is that the ratio of 1-2:1 is reacted in an aqueous medium in molar ratio, to obtain organic acid zinc alkanol amine compound, the alkanol
The general structure of amine is as follows:
Wherein R is methyl, ethyl or methylol.
2. organic acid zinc alkanol amine compound according to claim 1, it is characterised in that: the reaction is at 70-80 DEG C
It carries out, pH≤7 of reaction system.
3. organic acid zinc alkanol amine compound according to claim 1 or 2, it is characterised in that: can also be in the reaction system
Catalyst is added, the catalyst is sulfuric acid, nitric acid, hydrochloric acid or acetic acid, and the catalyst amount is the zinc salts of organic acid matter
The 0.1-2% of amount.
4. organic acid zinc alkanol amine compound according to claim 3, it is characterised in that: the zinc salts of organic acid is acetic acid
Zinc, zinc propionate, zinc lactate, zinc benzoate, 6- acetylamino sour zinc, zinc gluconate or zinc citrate.
5. organic acid zinc alkanol amine compound according to claim 4, it is characterised in that: the alkanolamine is 2- ammonia
Base -2- methyl-1,3-propanediol, 2- amino -2- ethyl -1,3- propylene glycol or trishydroxymethylaminomethane.
6. organic acid zinc alkanol amine compound according to claim 1, it is characterised in that: the alkanolamine is trihydroxy
Aminomethane.
7. a kind of heat stabilizer purposes of organic acid zinc alkanol amine compound, it is characterised in that: in chlorine-containing polymer process
It is middle that organic acid zinc alkanol amine compound described in any one of claims 1-6 is added as heat stabilizer.
8. a kind of preparation method of organic acid zinc alkanol amine compound, it is characterised in that preparation method according to claim 1
Preparation, and the temperature for controlling reaction system is 70-80 DEG C, pH≤7, to obtain the organic acid zinc alkanol amine compound.
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Denomination of invention: Organic acid zinc alkoxide amine complex and its use as a heat stabilizer Granted publication date: 20210302 Pledgee: Industrial and Commercial Bank of China Limited Chongqing Jiulongpo Branch Pledgor: CHONGQING TAIYUE NEW MATERIAL TECHNOLOGY Co.,Ltd. Registration number: Y2024500000091 |