CN100457810C - Orgnic rare earth thiolate composite stabilizator for halogen-containing polymer and application thereof - Google Patents
Orgnic rare earth thiolate composite stabilizator for halogen-containing polymer and application thereof Download PDFInfo
- Publication number
- CN100457810C CN100457810C CNB2006101324855A CN200610132485A CN100457810C CN 100457810 C CN100457810 C CN 100457810C CN B2006101324855 A CNB2006101324855 A CN B2006101324855A CN 200610132485 A CN200610132485 A CN 200610132485A CN 100457810 C CN100457810 C CN 100457810C
- Authority
- CN
- China
- Prior art keywords
- orgnic
- rare earth
- composite
- stabilizator
- thiolate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention discloses one kind of composite stabilizer of organic RE thiolate for halogen containing polymer and its application. The composite stabilizer is compounded with La, Ce, Pr or Nd thiolate formed with sulfhydryl compound and its mixture, organic metal stabilizer, lubricant, organic stabilizing assistant, etc. It has the features of long heat stabilizing period, low toxicity, etc. and may be used as the heat stabilizer in processing halogen containing polymer.
Description
Technical field
The present invention relates to chemical field, particularly a kind of Orgnic rare earth thiolate composite stabilizator and application thereof.
Background technology
Polymer containing halogen for example polyvinyl chloride etc. has superior corrosion resistance and mechanical property, cheap simultaneously, abundant raw material, manufacturing process maturation, and its goods are widely used in the every field of industrial and agricultural production.Yet polymer containing halogen adds that a fatal weakness is arranged man-hour is poor heat stability, so polymer containing halogen adds and must use thermo-stabilizer man-hour.Thermo-stabilizer commonly used in the polymer containing halogen course of processing has lead salts, organic tin, metallic soap class.But the lead salts thermo-stabilizer is poisoned bigger to human health, and environment is polluted.Costing an arm and a leg of organic tin thermo-stabilizer, and smell is poor, and only the minority kind is nontoxic.In recent years, along with the develop rapidly of plastic processing technology and people raising day by day to health requirements, the rules increasingly stringent of aspects such as whole world health, safety, environmental protection, " green " plastics have become the developing direction of 21 century plastics industry, efficient, multi-functional, nontoxic, the nuisanceless development trend that also becomes the polymer containing halogen thermo-stabilizer.Rare earth material starts from the seventies in last century as the research of polymer containing halogen thermo-stabilizer.Exploitation to rare earth composite stabilizer at present only limits to the rare earth organic carboxylate, this stablizer is nontoxic, tasteless, have good thermal stability and long-term weather resisteant, can replace lead salts, metallic soap class and part fully and replace organic tin, belong to the new generation of green environmentfriendly products; But the thermostable effect of this stablizer is quite limited, can't independently use, and is a kind of stablizer that helps stable form, and the organic carboxylate effect of its effect and alkaline-earth metal is suitable, does not embody the characteristic of rare earth metal, and thermal stability does not increase substantially.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, a kind of Heat stability is good, initial coloring is little, toxicity is little, cost is low Orgnic rare earth thiolate composite stabilizator are provided.
Another object of the present invention is to provide the application of a kind of above-mentioned Orgnic rare earth thiolate composite stabilizator in polymer containing halogen processing.
Purpose of the present invention is achieved through the following technical solutions:
A kind of Orgnic rare earth thiolate composite stabilizator is the mixture of Orgnic rare earth thiolate or Orgnic rare earth thiolate and active substance, comprises following components by part by weight:
Orgnic rare earth thiolate 1～50 weight part;
Organometallic stabilizer 0～40 weight part;
Lubricant 0～35 weight part;
Organic steady auxiliary agent 0～35 weight part of deciding.
Described Orgnic rare earth thiolate is by having HS (CH
2)
nR or HS (CH
2)
mThe thiolate of the sulfhydryl compound of COOR ' structure or the formed La of its mixture, Ce, Pr or Nd.Described HS (CH
2)
nR and HS (CH
2)
mThe sulfhydryl compound of COOR ' can directly be bought from the market or synthesize (org.Synth.1941,21,36 according to document; Org.Synth, Coll.Vol.3,363).
Described HS (CH
2)
nIn the R sulfhydryl compound, described R can be C
1～C
30Alkyl, C
6～C
18Contain the phenyl ring group or contain the alkyl of the heteroatomic straight or branched of N, O, S.Described C
1～C
30Alkyl preferable methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, hexadecyl or octadecyl.Described C
6～C
18Contain the preferred phenyl of phenyl ring group, tolyl, ethylbenzene base, n-proplbenzene base, cumyl, n-butyl benzene base, isobutylphenyl or trimethylphenylmethane base, benzyl, or beta-phenyl ethyl.Described n is 0,1,2,3,4,5,6 positive integers.
Described HS (CH
2)
mIn the COOR ' sulfhydryl compound, described R ' can be C
1～C
30Alkyl, the C of straight or branched
6～C
18Contain the phenyl ring group or contain the alkyl of the heteroatomic straight or branched of N, O, S.Described C
1～C
30Alkyl preferable methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, hexadecyl or the octadecyl of straight or branched.Described C
6～C
18Contain the preferred phenyl of phenyl ring group, tolyl, ethylbenzene base, n-proplbenzene base, cumyl, n-butyl benzene base, isobutylphenyl, trimethylphenylmethane base, benzyl or beta-phenyl ethyl.Described amino butyl of the preferred β of alkyl-thiomethyl ethyl, alpha-mercapto methyl, 4-or the Alpha-hydroxy ethyl that contains the heteroatomic straight or branched of N, O, S.Described m is 2,3,4,5,6 positive integers.
Described organometallic stabilizer can be organotin stabilizer or antimony organic stablizer.Two hydrocarbon pink salts of described organotin stabilizer preferred three (dodecyl) thiol-butyl tin, dibutyl tin laurate, two (dodecyl) mercaptan dibutyl tin, dianhydride three (dibutyl stannane glycol) or sulfydryl mercaptal.Preferred three (isooctyl mercaptoacetate) antimony of described antimony organic stablizer or three (lauryl mercaptan) antimony.
It is described that organic steady auxiliary to decide agent can be sulfur-bearing oxidation inhibitor, phenol antioxidant, epoxy compounds, organophosphite, polyvalent alcohol, beta-diketon or organic compounds containing nitrogen.
Described sulfur-bearing oxidation inhibitor can be thiodipropionate dilauryl, 3,3 '-thio-2 acid distearyl ester, 3,3 '-thio-2 acid, two cyclohexyls, 3,3 '-thio-2 acid, two oil base esters, 3,3 '-thio-2 acid ester in two ninth of the ten Heavenly Stems, 3,3 '-thio-2 acid didecyl ester, 3,3 '-thio-2 acid diethyl ester, 3-methylthio group propionic acid Lauryl Ester, 3-butylthio propionic acid Lauryl Ester, 3-lauryl thiohydracrylic acid Lauryl Ester, 3-octyl group thiohydracrylic acid phenyl ester or 3-dodecyl thiohydracrylic acid.
Described phenol antioxidant can be 2; the 6-ditertbutylparacresol; butylated hydroxy anisole; 4; 4 '-sulfo-two (6-tertiary butyl meta-cresol); 4; 4 '-the cyclohexylidene biphenol; 2; 5-two amyl hydroquinone; 4; 4 '-butylidene two (6-tertiary butyl meta-cresol); the quinhydrones single-benzyl ether; 2; 2 '-methylene radical-two (4-methyl-6-tert butyl phenol); 2; 6-butyl-4-oxygen in last of the ten Heavenly stems base phenol; the 2-tertiary butyl-4-dodecyloxy phenol; the 2-tertiary butyl-4-octadecane oxygen base phenol; 4; 4 '-methylene radical-two (2; the 6-DI-tert-butylphenol compounds); to chloro-phenol; N-lauryl oxygen base-p-aminophenol; 4; 4 '-sulfo-two (3 methy 6 tert butyl phenol); two (adjacent (1; 1; 3, the 3-tetramethyl butyl) phenol) sulfide; 4-ethanoyl-beta-resorcylic acid; A rank para-tert-butyl phenolic resin; 4-dodecyloxy-2-dihydroxy benaophenonel; palmitinic acid 3-hydroxyl-4-(phenylcarbonyl group) phenyl ester; 3-hydroxyl-4-(phenylcarbonyl group) phenylium dodecyl ester; or tert.-butyl phenol.
Described epoxy compounds can be an epoxidised soybean oil, epoxidation lard, the epoxidation sweet oil, epoxy linseed oil, the epoxidation Viscotrol C, epoxidation peanut oil, epoxidation Semen Maydis oil, epoxidation tung oil, the epoxidation Oleum Gossypii semen, epoxy chloropropane/bisphenol a resin, phenoxy group-propylene oxide, the butoxy propylene oxide, the inferior neo-pentyl oleic acid ester of epoxidation, the epoxystearic acid glycidyl ester, epoxidation a-alkene, the epoxidised soybean fatty acid glycidyl ester, the titanium dioxide dicyclopentadiene, epoxidation toluic acid butyl ester, Styrene oxide 98min., the titanium dioxide kautschin, Racemic glycidol, vinyl cyclohexene dioxide, the glycidyl ether of Resorcinol, the glycidyl ether of quinhydrones, 1, the glycidyl ether of 5-dihydroxy naphthlene, epoxy linseed oil lipid acid, glycidyl allyl ether, butylglycidyl ether, oxidizing ethyle alkyl, 4-(2,3-epoxy group(ing) propoxy-) methyl phenyl ketone, epoxidation Lay base oxygen, 2-ethyl-3-propyl group glycidamide, glycerol, the glycidyl ether of tetramethylolmethane and Sorbitol Powder, or 3,4-epoxy-cyclohexane-1,1-dimethanol two-9, the 10-epoxy stearate.
Described organophosphite can be the organophosphite that contains one or more groups in aryl, alkyl, aralkyl, the alkaryl.More specifically, described organophosphite can be a triphenyl phosphite, tricresyl phosphite, tricresyl phosphite (dimethyl benzene) ester, tributyl phosphate, the tricresyl phosphite monooctyl ester, tricresyl phosphite (dodecyl) ester, phosphorous acid monooctyl ester biphenyl ester, the dioctyl phosphite phenyl ester, tricresyl phosphite (octyl group benzene) ester, tricresyl phosphite (nonyl benzene) ester, Tribenzyl Phosphite, phosphorous acid butyl ester diformazan phenyl ester, phosphorous acid monooctyl ester two (octyl group benzene) ester, tricresyl phosphite (the 2-ethyl is own) ester, tricresyl phosphite, tricresyl phosphite (2-phenylcyclohexane) ester, tricresyl phosphite-a-naphthalene ester, tricresyl phosphite (phenyl benzene) ester, or tricresyl phosphite (2-benzene second) ester.
Described polyvalent alcohol can be that 2～32 carbon atoms and the combination of 2～12 polyvalent alcohols that hydroxyl constituted or molecular-weight average are that 100～10000 polyvinyl alcohol or molecular-weight average are 200～40000 polyethers.Described 2～32 carbon atoms and 2～12 polyvalent alcohol that hydroxyl constituted combinations can select propylene glycol, tris(2-hydroxy ethyl)isocyanurate, glycerol, propyleneglycoles, neopentyl glycol, kapok alcohol, Xylitol, arabitol, melampyrum, iditol, N.F,USP MANNITOL, Sorbitol Powder, three through methylpropane, tetramethylolmethane, dipentaerythritol or tripentaerythritol.
Described beta-diketon is diphenylpropane-1,3-dione(DPPO) or stearoyl benzoyl methane etc.
The maleimide that described organic compounds containing nitrogen can select for use Dyhard RU 100, trimeric cyanamide, urea, guanamines esterification thing, dimethyl beta-lactam, guanidine, thiocarbamide, 2-phenylindone, dihydropyridine, amino crotonate or N-to replace.
Described lubricant can be selected ester type waxes, lipid acid, Fatty Alcohol(C12-C14 and C12-C18), chloroflo or acid amides for use.
Described ester type waxes can be selected butyl ester, mono-glycerides, glyceryl ester, monooctyl ester, ninth of the ten Heavenly Stems ester, the certain herbaceous plants with big flowers ester of stearic acid, Toenol 1140, brown tung oil, decyl oleate, rice bran oil, Oleum Gossypii semen, hydrogenated cottonseed oil for use and di-carboxylic acid be arranged or low-molecular-weight polyester that polyvalent alcohol and lipid acid polycondensation form etc.
It is longer chain fatty acid of 12～31 etc. that described lipid acid can be selected carbonatoms for use.
It is long chain aliphatic alcohol of 12～31 etc. that described Fatty Alcohol(C12-C14 and C12-C18) can be selected carbonatoms for use.
Described chloroflo can be selected paraffin, Microcrystalline Wax, polyethylene wax, oxidized polyethlene wax, Poly Propylene Wax, its chlorinated polypropylene wax etc. for use.
Described acid amides can be selected laurylamide, stearylamide or sebacic acid acid amides etc. for use.
The shape of described Orgnic rare earth thiolate composite stabilizator can be Powdered or waxy solid, can be dispersed in the polymer containing halogen resin, and these shapes can be achieved by known physics mode on the multiple industry.
The application of Orgnic rare earth thiolate composite stabilizator of the present invention in polymer containing halogen processing, be that described Orgnic rare earth thiolate composite stabilizator is added in the polymer containing halogen, the consumption of described polymer containing halogen is 100 weight parts, the consumption of described Orgnic rare earth thiolate composite stabilizator is 0.1～8.5 weight part, preferred 1～4 weight part.
The application of described Orgnic rare earth thiolate composite stabilizator in polymer containing halogen processing can also be added one or more additives in pigment, filler, impact modifier, whipping agent, the right agent of resistance, static inhibitor, dyestuff, ultraviolet absorbers, antioxidant, viscosifying agent, the biocide in polymer containing halogen.
Described polymer containing halogen can be chlorinatedpolyethylene, chlorating natural rubber, chlorating synthetic rubber, rubber hydrochloride, chlorinated polyphenyl ethene, chlorinated polyvinyl chloride, polyvinyl bromide, fluorinated ethylene propylene or the vinyl chloride-base polymer that contains 14～75% (weight) chlorine.The monomer that described vinyl chloride-base polymer can be made up of separately vinylchlorid, the multipolymer that also can make by the monomer mixture that the vinylchlorid that accounts for total monomer 70% weight is at least formed.More specifically, but the multipolymer that the described monomer mixture of being made up of the vinylchlorid that accounts for total monomer 70% weight is at least made can be by vinylchlorid and account for the multipolymer that the ethylenic unsaturated materials of the copolymerization of total monomer 1～30% weight is made.Described ethylenic unsaturated materials can be selected vinyl-acetic ester for use, vinyl butyrate, vinyl benzoate, vinylidene chloride, DEF, ethyl maleate, other fumaric acid alkyl esters and toxilic acid alkyl ester, propionate, methyl acrylate, 2-EHA, butyl acrylate and other alkyl acrylates, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate and other alkyl methacrylates, a-Lv Daibingxisuan methyl esters, vinylbenzene, trieline, vinyl ether is (as EVE, the vinyl chloride ethyl ether, or vinyl phenyl ether), vinyl ketone is (as ethenyl methyl ketone, or ethenylphenyl ketone), 1-fluoro-2-vinylchlorid, vinyl cyanide, chloroacrylonitrile, inferior 2-propylene ester of oxalic acid and the typical multipolymer of the inferior 2-propylene ester of oxalic acid chloro.Inferior 2-propylene ester of described oxalic acid and the typical multipolymer of the inferior 2-propylene ester of oxalic acid chloro can be vinylchlorid-vinyl-acetic ester (96: 4 (weight ratio)), vinylchlorid-vinyl-acetic ester (87: 13), vinylchlorid-vinyl-acetic ester-Malaysia acid alcohol (86: 13: 1), vinylchlorid-vinylidene chloride (95: 5), vinylchlorid-DEF (95: 5) or vinylchlorid-2-EHA (80: 20).
The present invention compared with prior art has following advantage and effect:
(1) heat-stable time of this Orgnic rare earth thiolate composite stabilizator is long, and initial coloring is little, and toxicity is little.
(2) this stablizer is applied to can improve the stability of polymer containing halogen in the polymer containing halogen processing.
(3) this stablizer is applied to can realize plasticizing fast in the polymer containing halogen processing under 150 ℃ processing temperature, and power consumption of polymer processing is low.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but embodiments of the present invention are not limited thereto.
Embodiment 1
Three (lauryl mercaptan) lanthanum stablizer:
31.6g (0.1mol) Glacial acetic acid lanthanum, 18g (0.3mol) Virahol, 100ml toluene are joined in the reactor, under agitation condition, add 7.6g (0.3mol) sodium Metal 99.5, back flow reaction 2 hours.After the filtration, add 6.9g (0.3mol) lauryl mercaptan in filtrate, at room temperature stirring reaction is 1 hour; Then in rotatory evaporator, temperature is that 70 ℃, pressure are under the 4K handkerchief condition, revolves and steams 3 hours, makes white waxy three (lauryl mercaptan) lanthanum at last.
Embodiment 2
Three (isooctyl mercaptoacetate) lanthanum stablizer:
31.6g (0.1mol) Glacial acetic acid lanthanum, 14g (0.3mol) ethanol, 100ml benzene are joined in the reactor, under agitation condition, add 2.1g (0.3mol) metallic lithium, back flow reaction 2 hours.After the filtration, add 61g (0.3mol) isooctyl mercaptoacetate in filtrate, at room temperature stirring reaction is 1 hour; Then in rotatory evaporator, temperature is that 70 ℃, pressure are under the 4K handkerchief condition, revolves and steams 3 hours, makes little yellow waxy three (isooctyl mercaptoacetate) lanthanum at last.
Embodiment 3
Three (lauryl mercaptan) cerium stablizer:
31.6g (0.1mol) Glacial acetic acid cerium (III), 18g (0.3mol) Virahol, 100ml toluene are joined in the reactor, under agitation condition, add 7.6g (0.33mol) sodium Metal 99.5, back flow reaction 2 hours.After the filtration, add 6.9g (0.3mol) lauryl mercaptan in filtrate, at room temperature stirring reaction is 1 hour; Then in rotatory evaporator, temperature is that 70 ℃, pressure are under the 4K handkerchief condition, revolves and steams 3 hours, makes brown waxy three (lauryl mercaptan) cerium at last.
Embodiment 4
Three (lauryl mercaptan) praseodymium stablizer:
In there-necked flask, add 16.5g (0.06mol) anhydrous formic acid praseodymium, 100ml toluene and 4.8g (0.15mol) methyl alcohol.Slowly add 3.45g (0.15mol) sodium Metal 99.5.Logical stirring of inert gas 15 minutes, under 110 ℃, condensing reflux 2 hours.Reaction product is filtered down at 70 ℃, obtain settled solution (lanthanum isopropoxide/toluene).The gained settled solution added be equipped with in the 150ml single port flask of 30g (0.15mol) lauryl mercaptan, stirred 2 hours under the room temperature,, obtain the light green waxy solid in 80 ℃ of negative pressure evaporations 1 hour.This solid is washed with normal hexane, and filter 23 acquires 28g light green waxy three (lauryl mercaptan) praseodymium.
Embodiment 5
Three (isooctyl mercaptoacetate) neodymium stablizer:
31.6g (0.1mol) Glacial acetic acid neodymium, 18g (0.3mol) Virahol, 100ml benzene are joined in the reactor, under agitation condition, add 2.1g (0.3mol) metallic lithium, back flow reaction 2 hours.After the filtration, add 61g (0.3mol) isooctyl mercaptoacetate in filtrate, at room temperature stirring reaction is 1 hour; Then in rotatory evaporator, temperature is that 70 ℃, pressure are under the 4K handkerchief condition, revolves and steams 3 hours, makes little yellow waxy three (isooctyl mercaptoacetate) neodymium at last.
Embodiment 6
Three (isooctyl mercaptoacetate) lanthanum-epoxy soybean oil one package stabilizer:
Form by following components by part by weight:
Three (isooctyl mercaptoacetate) lanthanum, 2 weight part (phr
*)
Epoxidised soybean oil 1 weight part (phr)
(
*Be per handred, represent per 100 weight parts (PVC), down together.)
Embodiment 7
Three (isooctyl mercaptoacetate) lanthanum-polyethylene wax one package stabilizer:
Form by following components by part by weight:
Three (isooctyl mercaptoacetate) lanthanum 2 weight parts (phr)
Lubricant polyethylene wax 1 weight part (phr)
Embodiment 8
Three (isooctyl mercaptoacetate) lanthanum-polyethylene wax one package stabilizer:
Form by following components by part by weight:
Three (isooctyl mercaptoacetate) lanthanum 3 weight parts (phr)
Lubricant polyethylene wax 1 weight part (phr)
Embodiment 9
Three (isooctyl mercaptoacetate) lanthanum-phosphorous acid ester one package stabilizer:
Form by following components by part by weight:
Three (isooctyl mercaptoacetate) lanthanum 2 weight parts (phr)
Nontoxic phosphorous acid ester 1 weight part of MARK-1500 (phr)
Embodiment 10
Three (isooctyl mercaptoacetate) lanthanum-epoxy soybean oil-phosphorous acid ester one package stabilizer:
Form by following components by part by weight:
Three (isooctyl mercaptoacetate) lanthanum 2 weight parts (phr)
Epoxidised soybean oil 1.5 weight parts (phr)
Nontoxic phosphorous acid ester 0.5 weight part of MARK-1500 (phr)
Embodiment 11
Three (isooctyl mercaptoacetate) lanthanum-calcium/zinc composite stabilizer:
Form by following components by part by weight:
Three (isooctyl mercaptoacetate) lanthanum 1 weight part (phr)
Calcium stearate 0.42 weight part (phr)
Zinic stearas 0.21 weight part (phr)
Hydrotalcite 0.12 weight part (phr)
Dipentaerythritol 0.09 weight part (phr)
Paraffin 0.15 weight part (phr)
Test case 1: the test of dynamic thermal stability
60g is contained PVC and a certain amount of Orgnic rare earth thiolate composite thermal stabilizer mixes, join in the HAAKE torque rheometer.The mixing tank initial temperature is 180 ℃, and rotor speed is 50r/min.The thermo-stabilizer add-on is 3～4 parts/100 parts PVC parts by weight, phr).
Table 1 is the dynamic heat-stable time of Orgnic rare earth thiolate and one package stabilizer thereof.Obviously be better than calcium stearate, five Thiovanic acid monooctyl ester antimony and present widely used TM181 type organic mercaptan tin stablizer as can be seen from Table 1 the steady time of Orgnic rare earth thiolate and one package stabilizer thereof.
The dynamic heat-stable time of table 1 Orgnic rare earth thiolate composite stabilizator
| Thermo-stabilizer | Add-on/phr | Steady time/min |
| Calcium stearate * | 3 | 9.2 |
| Five isooctyl mercaptoacetate antimony * | 3 | 14 |
| TM181 dimethyl organic mercaptan tin * | 3 | 9.2 |
| Embodiment 1 | 3 | 14.6 |
| Embodiment 2 | 2 | 11.5 |
| Embodiment 2 | 3 | 17.6 |
| Embodiment 3 | 3 | 9.6 |
| Embodiment 4 | 3 | 9.1 |
| Embodiment 5 | 3 | 11.2 |
| Embodiment 6 | 3 | 16.4 |
| Embodiment 7 | 3 | 14.2 |
| Embodiment 8 | 4 | 22.3 |
| Embodiment 9 | 3 | 11.93 |
| Embodiment 10 | 4 | 10 |
| Embodiment 11 | 3 | 12.4 |
(
*Be Comparative Examples)
Claims (8)
1, a kind of Orgnic rare earth thiolate composite stabilizator is characterized in that: comprise following components by part by weight:
Orgnic rare earth thiolate 1～50 weight part;
Organometallic stabilizer＞0～40 weight part;
Lubricant＞0～35 weight part;
Organic auxiliary stabilizer＞0～35 weight part;
Wherein, described Orgnic rare earth thiolate is by having HS (CH
2)
nThe sulfhydryl compound of R structure or have HS (CH
2)
nR and HS (CH
2)
mThe thiolate of the formed La of the mixture of the sulfhydryl compound of COOR ' structure, Ce, Pr or Nd; Described HS (CH
2)
nIn the R sulfhydryl compound, described R is C
1～C
30Alkyl, C
6～C
18Contain the phenyl ring group or contain the alkyl of the heteroatomic straight or branched of N, O, S, described n is 0,1,2,3,4,5 or 6 positive integers; Described HS (CH
2)
mIn the COOR ' sulfhydryl compound, described R ' is C
1～C
30Alkyl, the C of straight or branched
6～C
18Contain the phenyl ring group or contain the alkyl of the heteroatomic straight or branched of N, O, S, described m is 2,3,4,5 or 6 positive integers.
2, Orgnic rare earth thiolate composite stabilizator according to claim 1 is characterized in that: described organometallic stabilizer is organotin stabilizer or antimony organic stablizer.
3, Orgnic rare earth thiolate composite stabilizator according to claim 1 is characterized in that: described organic auxiliary stabilizer is sulfur-bearing oxidation inhibitor, phenol antioxidant, epoxy compounds, organophosphite, polyvalent alcohol, beta-diketon or organic compounds containing nitrogen.
4, Orgnic rare earth thiolate composite stabilizator according to claim 1 is characterized in that: described lubricant is ester type waxes, lipid acid, Fatty Alcohol(C12-C14 and C12-C18), chloroflo or acid amides.
5, each described Orgnic rare earth thiolate composite stabilizator of a kind of claim 1～4 is used in the halogenic polymer course of processing, it is characterized in that: be that described Orgnic rare earth thiolate composite stabilizator is added in the polymer containing halogen, the consumption of described polymer containing halogen is 100 weight parts, and the consumption of described Orgnic rare earth thiolate composite stabilizator is 0.1～8.5 weight part.
6, Orgnic rare earth thiolate composite stabilizator according to claim 5 is used in the halogenic polymer course of processing, it is characterized in that: the consumption of described Orgnic rare earth thiolate composite stabilizator is 1～4 weight part.
7, Orgnic rare earth thiolate composite stabilizator according to claim 5 is used in the halogenic polymer course of processing, it is characterized in that: described polymer containing halogen is chlorinatedpolyethylene, chlorating natural rubber, chlorating synthetic rubber, rubber hydrochloride, chlorinated polyphenyl ethene, chlorinated polyvinyl chloride, polyvinyl bromide, fluorinated ethylene propylene or the vinyl chloride-base polymer that contains 14～75% (weight) chlorine.
8, Orgnic rare earth thiolate composite stabilizator according to claim 5 is used in the halogenic polymer course of processing, it is characterized in that: can also add one or more additives in pigment, filler, impact modifier, whipping agent, fire retardant, static inhibitor, dyestuff, ultraviolet absorbers, antioxidant, viscosifying agent, the biocide in polymer containing halogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101324855A CN100457810C (en) | 2006-12-31 | 2006-12-31 | Orgnic rare earth thiolate composite stabilizator for halogen-containing polymer and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101324855A CN100457810C (en) | 2006-12-31 | 2006-12-31 | Orgnic rare earth thiolate composite stabilizator for halogen-containing polymer and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN100999591A CN100999591A (en) | 2007-07-18 |
| CN100457810C true CN100457810C (en) | 2009-02-04 |
Family
ID=38258423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101324855A Expired - Fee Related CN100457810C (en) | 2006-12-31 | 2006-12-31 | Orgnic rare earth thiolate composite stabilizator for halogen-containing polymer and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100457810C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030898B (en) * | 2011-09-30 | 2015-10-28 | 贵州大学 | A kind of PVC rare earth thermal stabilizer and preparation method thereof |
| CN102417676B (en) * | 2011-11-16 | 2013-09-11 | 山东瑞丰高分子材料股份有限公司 | Composite stabilizing agent for transparent polyvinyl chloride (PVC) material and preparation method thereof |
| CN102643494B (en) * | 2012-05-10 | 2014-04-16 | 唐山师范学院 | Preparation method and applications of calcium/zinc composite thermal stabilizing additive used for polyvinyl chloride |
| CN103524962B (en) * | 2012-07-05 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of CPVC composition and method of making the same with good thermal stability energy |
| CN103073820A (en) * | 2013-01-18 | 2013-05-01 | 内蒙古科技大学 | Rare earth composite heat stabilizer for PVC |
| CN106317721A (en) * | 2015-06-17 | 2017-01-11 | 中国石油化工股份有限公司 | CPVC injection molding special material with high thermal stability and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4162339A (en) * | 1975-07-18 | 1979-07-24 | James Hunkins | Newsprint coupon separator |
| EP0108023A1 (en) * | 1982-10-08 | 1984-05-09 | Rhone-Poulenc Chimie | Process for the stabilization of vinyl chloride polymers |
| US4559372A (en) * | 1983-10-21 | 1985-12-17 | Rhone-Poulenc Specialities Chimiques | Fireproofed polyamide compositions |
| US4985485A (en) * | 1988-10-13 | 1991-01-15 | Rhone-Poulenc Chimie | Fire-resistant polyamide compositions |
| US5143959A (en) * | 1990-04-20 | 1992-09-01 | Rhone-Poulenc Chimie | Compositions for use with chlorinated polymers |
| US5194470A (en) * | 1990-04-20 | 1993-03-16 | Rhone-Poulenc Chimie | Compositions for stabilizing chlorinated polymers |
| US5278218A (en) * | 1990-12-10 | 1994-01-11 | Rhone-Poulenc Chimie | Zinc stannate/zinc hydroxystannate heat-stabilized chloropolymers |
| US5332772A (en) * | 1993-05-05 | 1994-07-26 | Morton International, Inc. | Combination heat stabilizer/lubricant for PVC processing and method for producing the same |
-
2006
- 2006-12-31 CN CNB2006101324855A patent/CN100457810C/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4162339A (en) * | 1975-07-18 | 1979-07-24 | James Hunkins | Newsprint coupon separator |
| EP0108023A1 (en) * | 1982-10-08 | 1984-05-09 | Rhone-Poulenc Chimie | Process for the stabilization of vinyl chloride polymers |
| US4559372A (en) * | 1983-10-21 | 1985-12-17 | Rhone-Poulenc Specialities Chimiques | Fireproofed polyamide compositions |
| US4985485A (en) * | 1988-10-13 | 1991-01-15 | Rhone-Poulenc Chimie | Fire-resistant polyamide compositions |
| US5143959A (en) * | 1990-04-20 | 1992-09-01 | Rhone-Poulenc Chimie | Compositions for use with chlorinated polymers |
| US5194470A (en) * | 1990-04-20 | 1993-03-16 | Rhone-Poulenc Chimie | Compositions for stabilizing chlorinated polymers |
| US5278218A (en) * | 1990-12-10 | 1994-01-11 | Rhone-Poulenc Chimie | Zinc stannate/zinc hydroxystannate heat-stabilized chloropolymers |
| US5332772A (en) * | 1993-05-05 | 1994-07-26 | Morton International, Inc. | Combination heat stabilizer/lubricant for PVC processing and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100999591A (en) | 2007-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100457810C (en) | Orgnic rare earth thiolate composite stabilizator for halogen-containing polymer and application thereof | |
| CN100480309C (en) | Composite stabilizer of metal salt of organic carboxylic acid containing sulfur in use for polymer containing halogen, and application thereof | |
| US4221687A (en) | Anti-yellowing composition | |
| CN1217973C (en) | Process for producing poly(1,4-cyclohexylenedimethylene 1,4-cyclohexanedicarboxylate) and the reactor grade polyester therefrom | |
| EP0739377B1 (en) | Polyol ester pvc plasticizers | |
| CN102391592B (en) | Environmental-friendly calcium-zinc stabilizer for PVC (Polyvinyl Chloride) rolling film and preparation method thereof | |
| CN106164164A (en) | Vinyl chloride resin plasticizer containing non-phthalic acid system ester and the vinyl chloride resin composition containing this plasticizer | |
| DE2550507A1 (en) | ORGANOCINAL SULFURIOUS COMPOUNDS | |
| CN106380729B (en) | Novel PVC heat stabilizer | |
| JP2013505349A (en) | Flame retardant and optically clear thermoplastic molding composition | |
| CN1757665A (en) | Thermal stabilizer compositions for halogen-containing vinyl polymers | |
| CN1715381A (en) | Lubricating oil composite stabilizer and stable hydrogenation lubricating oil composition | |
| WO2002070625A1 (en) | Phosphite ester additive compositions | |
| CN110698867A (en) | Preparation method of calcium-zinc stabilizer for shoe material | |
| CN1232050A (en) | Synergistic blend of metal-based stabilizer or lewis acid and free mercaptan for enhanced PVC stabilization | |
| CN113004506A (en) | Preparation method and application of heat-resistant and migration-resistant environment-friendly plasticizer | |
| TW200904832A (en) | A stabilizer composition for vinylchloride type resin and vinylchloride type resin composition containing the same | |
| TW568943B (en) | Carboxyl-functional polyester resin, and power paint formulation containing the resin and its preparation | |
| CN1757669A (en) | Thermal stabilizer composition for halogen-containing vinyl polymers | |
| CN100432129C (en) | Thermal stabilizer compositions for halogen-containing vinyl polymers | |
| CN1536015A (en) | Composite thermal stabilizing agent for polyvinyl chloride and its derivative composition | |
| US3417039A (en) | Chlorine containing resins stabilized with mixtures comprising not more than two metal salts, a polyol and a sulfur containing compound | |
| CN1350027A (en) | Polymer composition containing halogen stabilized by crypto-thio-alcohol and mixture of zinc carboxylate and zinc chloride | |
| CN1629218A (en) | Thermal stabilizer composition for halogen-containing vinyl polymers | |
| CN102300923B (en) | Vinyl Chloride Resin Composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090204 Termination date: 20141231 |
|
| EXPY | Termination of patent right or utility model |