CN114437475A - Preparation method of reverse ester tin stabilizer - Google Patents
Preparation method of reverse ester tin stabilizer Download PDFInfo
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- CN114437475A CN114437475A CN202210259655.5A CN202210259655A CN114437475A CN 114437475 A CN114437475 A CN 114437475A CN 202210259655 A CN202210259655 A CN 202210259655A CN 114437475 A CN114437475 A CN 114437475A
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- tin
- ester
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- fatty acid
- reverse ester
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 150000002148 esters Chemical class 0.000 title claims abstract description 48
- 239000003381 stabilizer Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims abstract description 39
- -1 fatty acid mercaptoethanol ester Chemical class 0.000 claims abstract description 27
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 25
- 239000000194 fatty acid Substances 0.000 claims abstract description 25
- 229930195729 fatty acid Natural products 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 13
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 10
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 25
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 12
- 229910052945 inorganic sulfide Inorganic materials 0.000 claims description 11
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 11
- YFRLQYJXUZRYDN-UHFFFAOYSA-K trichloro(methyl)stannane Chemical compound C[Sn](Cl)(Cl)Cl YFRLQYJXUZRYDN-UHFFFAOYSA-K 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 150000004763 sulfides Chemical class 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 8
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 8
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- INTLMJZQCBRQAT-UHFFFAOYSA-K trichloro(octyl)stannane Chemical compound CCCCCCCC[Sn](Cl)(Cl)Cl INTLMJZQCBRQAT-UHFFFAOYSA-K 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 2
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical group CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000004040 coloring Methods 0.000 abstract description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 10
- 229920000915 polyvinyl chloride Polymers 0.000 description 10
- KGHLYBKDIPRXHA-UHFFFAOYSA-N octyl(oxo)tin Chemical compound CCCCCCCC[Sn]=O KGHLYBKDIPRXHA-UHFFFAOYSA-N 0.000 description 7
- 229940049964 oleate Drugs 0.000 description 7
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 6
- JHHJZXAFNAJSCA-UHFFFAOYSA-N methyl(oxo)tin Chemical compound C[Sn]=O JHHJZXAFNAJSCA-UHFFFAOYSA-N 0.000 description 6
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 3
- QWHHBVWZZLQUIH-UHFFFAOYSA-N 2-octylbenzenesulfonic acid Chemical compound CCCCCCCCC1=CC=CC=C1S(O)(=O)=O QWHHBVWZZLQUIH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000013475 authorization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013058 crude material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Images
Classifications
-
- 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
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
- C08K5/58—Organo-tin compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/226—Compounds with one or more Sn-S linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The invention discloses a preparation method of a reverse ester tin stabilizer, belonging to the technical field of stabilizers, the preparation method of the reverse ester tin stabilizer comprises the following components by equal mass: 30-40 parts of organic tin oxide and 40-60 parts of fatty acid mercaptoethanol ester; a preparation method of a reverse ester tin stabilizer comprises the following steps: m1, synthetic organotin oxide; m2, synthetic fatty acid mercaptoethanol ester; m3, synthetic reverse ester tin stabilizer; by adopting the organic tin oxide to react with the fatty acid reverse ester, the process is simple, the raw material transportation and use are safe and convenient, and the obtained product reverse ester tin has large molecular weight, good lubricity, low tin content and good initial coloring, is particularly suitable for processing PVC pipes, profiles and foamed products, is suitable for industrial production of enterprises, can be widely applied to industrial production, and has great advantages in the application of PVC pipe profiles.
Description
Technical Field
The invention relates to the technical field of stabilizers, and particularly relates to a preparation method of a reverse ester tin stabilizer.
Background
PVC is a heat sensitive resin that is second only to PE in thermoplastics in world years. The product has the advantages of easy regulation of hardness, high mechanical property, corrosion resistance, good electrical insulation, high transparency and the like, and has the conditions of low price, rich resources, mature manufacturing process and the like, so the product has very wide application in the production fields of industry, agriculture and the like. Polyvinyl chloride has poor stability to light and heat, begins to decompose at about 160 ℃ to generate hydrogen chloride, and the released hydrogen chloride accelerates the decomposition of PVC to cause discoloration, and physical and mechanical properties are rapidly reduced.
The processing temperature of PVC in the prior art is generally above 160 ℃, so that a stabilizer must be added in practical application to improve the stability of the PVC to heat and light, and lead salt stabilizers are used in the processing process of most of PVC pipes, profiles, foams and other materials at present. However, with the enhancement of environmental awareness, lead salt stabilizers are gradually eliminated.
Through search, the prior reverse ester tin synthesis technology at present comprises the following steps: a sulfo (combined) tin reverse ester, a preparation method and an application authorization notice number are as follows: CN102584889B, adopting methyl tin chloride aqueous solution, reverse ester and ammonia water to carry out esterification reaction, but the prior art adopts liquid methyl tin chloride as raw material, the liquid methyl tin chloride is a dangerous chemical and is inconvenient to transport and use, and the reaction process has the problem of low yield, so that the reverse ester tin stabilizer with simple process and safe transportation is particularly important.
Disclosure of Invention
The invention aims to solve the problems that dangerous chemicals are used as raw materials, transportation and use are inconvenient, and the yield is low in the reaction process in the prior art, and provides a preparation method of a reverse ester tin stabilizer.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the tin retro-ester stabilizer comprises the following components in parts by mass: 30-40 parts of organic tin oxide and 40-60 parts of fatty acid mercaptoethanol ester.
Preferably, the preparation steps are as follows:
m1, synthetic organotin oxide;
m2, synthetic fatty acid mercaptoethanol ester;
m3, synthetic reverse ester tin stabilizer.
Preferably, the organotin oxides comprise the following components: 30-40 parts of organic tin chloride, 20-30 parts of liquid alkali solution, 20-30 parts of inorganic sulfide salt solution and 8-10 parts of water;
the preparation steps of the organotin oxide are as follows:
a1, putting organotin chloride into a reaction kettle, and preparing an aqueous solution with the chlorine content of 10-25%;
a2, preparing 10-20% of liquid alkali solution;
a3, preparing 10-20% of inorganic sulfide salt solution;
a4, dropwise adding the prepared liquid alkali solution and inorganic sulfide solution into a reaction kettle, and heating to 50-60 ℃;
a5, controlling the ph value in the reaction kettle to be 7-8;
a6, keeping the temperature at 50-60 ℃ and reacting for 1-2 h;
a7, standing and layering;
a8, taking the layered solid to obtain a coarse material, and washing the coarse material by using water;
and A9, taking the washed coarse material, and carrying out filter pressing to obtain the organic tin oxide.
Preferably, the fatty acid mercaptoethanol ester comprises the following components: 50-60 parts of fatty acid and 30-40 parts of mercaptoethanol; 5-10 parts of a catalyst;
the preparation steps of the fatty acid mercaptoethanol ester are as follows:
b1, putting fatty acid into a reaction kettle, and heating to 50-70 ℃;
b2, putting mercaptoethanol and a catalyst into a reaction kettle for mixing;
b3, heating to 60-70 ℃, and reacting for 2-4h under the condition of heat preservation;
b4, measuring the acid value in the reaction kettle, heating to 70-80 ℃ for vacuum dehydration for 1-2h when the acid value is reduced to 10-15 mgKOH/g;
b5, filtering to obtain the fatty acid mercaptoethanol ester.
Preferably, the molar ratio of organotin chloride ions to mercaptoethanol fatty acid ester is from 0.9: 1.
preferably, the organotin chloride may be any one of methyltin chloride, butyltin chloride and octyltin chloride.
Preferably, the liquid alkali can be any one of sodium hydroxide and ammonia water, and the inorganic sulfide salt can be one or two of sodium sulfide, sodium hydrosulfide and ammonium sulfide.
Preferably, the fatty acid can be one or two of oleic acid, isooctanoic acid and caprylic-capric acid.
Preferably, the catalyst is methyl benzene sulfonic acid or sulfuric acid.
Preferably, the following detailed steps are included:
s1, putting 40-60 parts of fatty acid mercaptoethanol ester into a reaction kettle, and heating to 50-70 ℃ for reaction;
s2, putting 30-40 parts of organic tin oxide into a reaction kettle, heating to 70-80 ℃ and reacting for 2-4 h;
s3, keeping the reaction kettle dehydrated for 1-3h in the environment with the Maifand vacuum degree of 100 and the temperature of 70-80 ℃;
s4, filtering to obtain the reverse ester tin stabilizer.
Compared with the prior art, the invention provides a preparation method of the reverse ester tin stabilizer, which has the following beneficial effects:
the reverse ester tin stabilizer has the advantages that the organic tin oxide and the fatty acid reverse ester are adopted for reaction, the process is simple, the raw material transportation and the use are safe and convenient, the obtained product reverse ester tin has large molecular weight, good lubricity, low tin content and good initial coloring, is particularly suitable for processing PVC pipes, sectional materials and foaming material products, is suitable for industrial production of enterprises, can be widely applied to industrial production, and has great advantages in the application of PVC pipe sectional materials.
Drawings
FIG. 1 is a flow chart of a preparation process of tin reverse ester according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention.
Example 1:
the preparation method of the tin retro-ester stabilizer comprises the following components in parts by mass: 35 parts of methyl tin oxide and 50 parts of isooctanoate mercaptoethanol ester.
A preparation method of a reverse ester tin stabilizer comprises the following steps:
m1, synthetic methyl tin oxide;
m2, synthesizing isooctanoate mercaptoethanol ester;
m3, synthetic reverse ester tin stabilizer.
The methyl tin oxide comprises the following components: 35 parts of methyl tin chloride, 25 parts of sodium hydroxide solution, 25 parts of inorganic sulfide salt solution and 9 parts of water;
the preparation steps of the methyl tin oxide are as follows:
a1, putting 200g of methyl tin chloride into a reaction kettle, and preparing an aqueous solution with the chlorine content of 15%;
a2, preparing 250ml of 10% sodium hydroxide solution;
a3, preparing 150ml of sodium sulfide solution with the concentration of 10 percent;
a4, dropwise adding the prepared sodium hydroxide solution and sodium sulfide solution into a reaction kettle, and heating to 55 ℃;
a5, controlling the ph value in the reaction kettle to be 8;
a6, keeping the temperature at 55 ℃ and reacting for 1 h;
a7, standing and layering;
a8, taking the layered solid to obtain a coarse material, and washing the coarse material by using water;
and A9, taking the washed crude material, and carrying out filter pressing to obtain the methyl tin oxide.
The isooctanoic acid mercaptoethanol ester comprises the following components: 55 parts of isooctanoic acid and 35 parts of mercaptoethanol; 6 parts of methylbenzenesulfonic acid;
the preparation steps of the isooctanoate mercaptoethanol ester are as follows:
b1, putting 303g of isooctanoic acid into a reaction kettle, and heating to 60 ℃;
b2, taking 156g of mercaptoethanol and 6g of methylbenzenesulfonic acid, and mixing in a reaction kettle;
b3, heating to 65 ℃, and reacting for 3 hours under the condition of heat preservation;
b4, measuring the acid value in the reaction kettle, heating to 75 ℃ until the acid value is reduced to 10mgKOH/g
Dehydrating for 2h in vacuum;
b5, filtering to obtain colorless and transparent mercapto ethanol isooctanoate.
The molar ratio of the methyl tin chloride ions to the mercaptoethanol isooctanoate is 0.9: 1.
the preparation method of the reverse ester tin stabilizer comprises the following detailed steps:
s1, putting 400g of mercaptoethanol isooctanoate into a reaction kettle, and heating to 60 ℃ for reaction;
s2, putting 120g of methyl tin oxide into a reaction kettle, and heating to 75 ℃ for reaction for 3 hours;
s3, keeping the reaction kettle dehydrated for 2 hours in an environment with the Mains vacuum degree of 200pa and the temperature of 75 ℃;
s4, filtering to obtain colorless and transparent tin methyl reverse ester.
Example 2:
the preparation method of the tin retro-ester stabilizer comprises the following components in parts by mass: 35 parts of monobutyl tin oxide and 50 parts of mercaptoethanol oleate.
A preparation method of a reverse ester tin stabilizer comprises the following steps:
m1, synthetic monobutyl tin oxide;
m2, synthesizing mercaptoethanol oleate;
m3, synthetic reverse ester tin stabilizer.
The monobutyl tin oxide comprises the following components: 35 parts of methyl tin chloride, 25 parts of sodium hydroxide solution, 25 parts of inorganic sulfide salt solution and 9 parts of water;
the preparation steps of the monobutyl tin oxide are as follows:
a1, putting 200g of methyl tin chloride into a reaction kettle, and preparing an aqueous solution with the chlorine content of 15%;
a2, preparing 250ml of 10% sodium hydroxide solution;
a3, preparing 150ml of sodium sulfide solution with the concentration of 10 percent;
a4, dropwise adding the prepared sodium hydroxide solution and sodium sulfide solution into a reaction kettle, and heating to 55 ℃;
a5, controlling the ph value in the reaction kettle to be 8;
a6, keeping the temperature at 55 ℃ and reacting for 1 h;
a7, standing and layering;
a8, taking the layered solid to obtain a coarse material, and washing the coarse material by using water;
and A9, taking the washed coarse material and carrying out filter pressing to obtain the monobutyl tin oxide.
The mercaptoethanol oleate comprises the following components: 55 parts of oleic acid and 35 parts of mercaptoethanol; 6 parts of methylbenzenesulfonic acid;
the preparation steps of the mercaptoethanol oleate are as follows:
b1, putting 595g of oleic acid into a reaction kettle, and heating to 60 ℃;
b2, putting 156g of mercaptoethanol and 12g of methylbenzenesulfonic acid into a reaction kettle for mixing;
b3, heating to 65 ℃, and reacting for 3 hours under the condition of heat preservation;
b4, measuring the acid value in the reaction kettle, heating to 75 ℃ until the acid value is reduced to 10mgKOH/g
Dehydrating for 2h in vacuum;
b5, filtering to obtain light yellow transparent mercaptoethanol oleate.
The molar ratio of the methyl tin chloride ions to the mercaptoethanol oleate is 0.9: 1.
the preparation method of the monobutyl retro-ester tin stabilizer comprises the following detailed steps:
s1, putting 400g of mercaptoethanol oleate into a reaction kettle, and heating to 60 ℃ for reaction;
s2, putting 120g of monobutyl tin oxide into a reaction kettle, heating to 75 ℃ and reacting for 3 hours;
s3, keeping the reaction kettle dehydrated for 2 hours in an environment with the Mains vacuum degree of 200pa and the temperature of 75 ℃;
s4, filtering to obtain light yellow transparent tin methyl reverse ester.
Example 3:
the preparation method of the tin retro-ester stabilizer comprises the following components in parts by mass: 35 parts of octyl tin oxide and 50 parts of octyl decanoic acid mercaptoethanol ester.
A preparation method of a reverse ester tin stabilizer comprises the following steps:
m1, synthetic octyl tin oxide;
m2, synthesizing caprylic/capric acid mercaptoethanol ester;
m3, synthetic reverse ester tin stabilizer.
The octyl tin oxide comprises the following components: 35 parts of octyl tin chloride, 25 parts of sodium hydroxide solution, 25 parts of inorganic sulfide salt solution and 9 parts of water;
the preparation steps of octyl tin oxide are as follows:
a1, putting 200g of octyl tin chloride into a reaction kettle, and preparing an aqueous solution with the chlorine content of 15%;
a2, preparing 250ml of 10% sodium hydroxide solution;
a3, preparing 150ml of sodium sulfide solution with the concentration of 10 percent;
a4, dropwise adding the prepared sodium hydroxide solution and sodium sulfide solution into a reaction kettle, and heating to 55 ℃;
a5, controlling the ph value in the reaction kettle to be 8;
a6, keeping the temperature at 55 ℃ and reacting for 1 h;
a7, standing and layering;
a8, taking the layered solid to obtain a coarse material, and washing the coarse material by using water;
and A9, taking the washed coarse material and carrying out filter pressing to obtain the octyl tin oxide.
The octyl and decyl mercapto alcohol ester comprises the following components: 55 parts of caprylic-capric acid and 35 parts of mercaptoethanol; 6 parts of octyl benzene sulfonic acid;
the preparation method of the mercaptoethanol ester of the octyl and decyl acid comprises the following steps:
b1, taking 330g of caprylic-capric acid, putting the caprylic-capric acid into a reaction kettle, and heating to 60 ℃;
b2, taking 156g of mercaptoethanol and 6g of octyl benzene sulfonic acid, and mixing in a reaction kettle;
b3, heating to 65 ℃, and reacting for 3 hours under the condition of heat preservation;
b4, measuring the acid value in the reaction kettle, heating to 75 ℃ until the acid value is reduced to 10mgKOH/g
Dehydrating for 2h in vacuum;
b5, filtering to obtain light yellow transparent octyl and decyl mercapto ethanol ester.
The mol ratio of octyl tin chloride to mercaptoethanol octyldecanoate is 0.9: 1.
the preparation method of the reverse ester tin stabilizer comprises the following detailed steps:
s1, putting 400g of mercaptoethanol ester of octyl and decyl acid into a reaction kettle, and heating to 60 ℃ for reaction;
s2, taking 120g of octyl tin oxide, putting the octyl tin oxide into a reaction kettle, heating to 75 ℃, and reacting for 3 hours;
s3, keeping the reaction kettle dehydrated for 2 hours in an environment with the Mains vacuum degree of 200pa and the temperature of 75 ℃;
s4, filtering to obtain light yellow transparent octyl reverse ester tin.
The preparation process flow chart of the reverse ester tin is shown in the figure 1 in detail.
As can be seen from examples 1 to 3 and fig. 1, the reverse ester tin stabilizer has the advantages that the organic tin oxide is adopted to react with the fatty acid reverse ester, the process is simple, the raw material transportation is safe and convenient, the obtained product reverse ester tin has large molecular weight, good lubricity, low tin content and good initial coloring, is particularly suitable for processing PVC pipes, profiles and foamed products, is suitable for industrial production of enterprises, can be widely applied to industrial production, and has great advantages in PVC pipe profile application.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical scope of the present invention and the equivalent alternatives or modifications according to the technical solution and the inventive concept of the present invention within the technical scope of the present invention.
Claims (10)
1. The preparation method of the tin reverse ester stabilizer is characterized in that the tin reverse ester stabilizer comprises the following components in equal mass: 30-40 parts of organic tin oxide and 40-60 parts of fatty acid mercaptoethanol ester.
2. The preparation method of the reverse ester tin stabilizer according to claim 1, comprising the following steps:
m1, synthetic organotin oxide;
m2, synthetic fatty acid mercaptoethanol ester;
m3, synthetic reverse ester tin stabilizer.
3. The method for preparing the reverse ester tin stabilizer according to claim 2, wherein the organotin oxide comprises the following components: 30-40 parts of organic tin chloride, 20-30 parts of liquid alkali solution, 20-30 parts of inorganic sulfide salt solution and 8-10 parts of water;
the preparation steps of the organotin oxide are as follows:
a1, putting organotin chloride into a reaction kettle, and preparing an aqueous solution with the chlorine content of 10-25%;
a2, preparing 10-20% of liquid alkali solution;
a3, preparing 10-20% of inorganic sulfide salt solution;
a4, dropwise adding the prepared liquid alkali solution and inorganic sulfide solution into a reaction kettle, and heating to 50-60 ℃;
a5, controlling the ph value in the reaction kettle to be 7-8;
a6, keeping the temperature at 50-60 ℃ and reacting for 1-2 h;
a7, standing and layering;
a8, taking the layered solid to obtain a coarse material, and washing the coarse material by using water;
and A9, taking the washed coarse material, and carrying out filter pressing to obtain the organic tin oxide.
4. The method of preparing the reverse ester tin stabilizer of claim 2, wherein the fatty acid mercaptoethanol ester comprises the following components: 50-60 parts of fatty acid and 30-40 parts of mercaptoethanol; 5-10 parts of a catalyst;
the preparation steps of the fatty acid mercaptoethanol ester are as follows:
b1, putting fatty acid into a reaction kettle, and heating to 50-70 ℃;
b2, putting mercaptoethanol and a catalyst into a reaction kettle for mixing;
b3, heating to 60-70 ℃, and reacting for 2-4h under the condition of heat preservation;
b4, measuring the acid value in the reaction kettle, heating to 70-80 ℃ for vacuum dehydration for 1-2h when the acid value is reduced to 10-15 mgKOH/g;
b5, filtering to obtain the fatty acid mercaptoethanol ester.
5. The method for preparing the reverse ester tin stabilizer according to claim 1, wherein the molar ratio of the organotin chloride ions to the fatty acid mercaptoethanol ester is 0.9: 1.
6. the method for preparing the reverse ester tin stabilizer according to claim 2, wherein the organotin chloride is any one of methyl tin chloride, butyl tin chloride and octyl tin chloride.
7. The method for preparing the reverse ester tin stabilizer according to claim 3, wherein the liquid alkali can be any one of sodium hydroxide and ammonia water, and the inorganic sulfide salt can be one or two of sodium sulfide, sodium hydrosulfide and ammonium sulfide.
8. The method for preparing reverse ester tin stabilizer according to claim 4, wherein the fatty acid can be one or two of oleic acid, isooctanoic acid and caprylic-capric acid.
9. The method of claim 4, wherein the catalyst is toluene sulfonic acid or sulfuric acid.
10. The method of preparing the reverse ester tin stabilizer of claim 2, comprising the following detailed steps:
s1, putting 40-60 parts of fatty acid mercaptoethanol ester into a reaction kettle, and heating to 50-70 ℃ for reaction;
s2, putting 30-40 parts of organic tin oxide into a reaction kettle, heating to 70-80 ℃ and reacting for 2-4 h;
s3, keeping the reaction kettle dehydrated for 1-3h in the environment with the Maifand vacuum degree of 100 and the temperature of 70-80 ℃;
s4, filtering to obtain the reverse ester tin stabilizer.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115322218A (en) * | 2022-08-03 | 2022-11-11 | 湖北犇星新材料股份有限公司 | Reverse ester type mercaptoethanol stearate methyl tin and preparation method thereof |
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| CN102250136A (en) * | 2011-05-13 | 2011-11-23 | 浙江海普顿化工科技有限公司 | Preparation method of methyltin mercaptide |
| CN102584889A (en) * | 2011-12-26 | 2012-07-18 | 湖北犇星化工有限责任公司 | Sulfo-(combination) tin reverse-ester, preparation method and application |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250136A (en) * | 2011-05-13 | 2011-11-23 | 浙江海普顿化工科技有限公司 | Preparation method of methyltin mercaptide |
| CN102584889A (en) * | 2011-12-26 | 2012-07-18 | 湖北犇星化工有限责任公司 | Sulfo-(combination) tin reverse-ester, preparation method and application |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115322218A (en) * | 2022-08-03 | 2022-11-11 | 湖北犇星新材料股份有限公司 | Reverse ester type mercaptoethanol stearate methyl tin and preparation method thereof |
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