CN105949667B - A kind of organic barium of beta diketone class/zinc PVC heat stabilizer and preparation method thereof - Google Patents
A kind of organic barium of beta diketone class/zinc PVC heat stabilizer and preparation method thereof Download PDFInfo
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- CN105949667B CN105949667B CN201610442128.2A CN201610442128A CN105949667B CN 105949667 B CN105949667 B CN 105949667B CN 201610442128 A CN201610442128 A CN 201610442128A CN 105949667 B CN105949667 B CN 105949667B
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- 239000012760 heat stabilizer Substances 0.000 title claims abstract description 32
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052788 barium Inorganic materials 0.000 title claims abstract description 29
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 29
- 239000011701 zinc Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 125000005594 diketone group Chemical class 0.000 title abstract 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000002425 crystallisation Methods 0.000 claims abstract description 16
- 230000008025 crystallization Effects 0.000 claims abstract description 16
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 15
- 150000001553 barium compounds Chemical class 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- 230000004044 response Effects 0.000 claims description 24
- 239000012065 filter cake Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 14
- 150000003751 zinc Chemical class 0.000 claims description 12
- 159000000009 barium salts Chemical class 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 5
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical group [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 4
- 229910001626 barium chloride Inorganic materials 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims 1
- 239000004246 zinc acetate Substances 0.000 claims 1
- 239000003381 stabilizer Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- -1 diketone class compound Chemical class 0.000 abstract description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 33
- 229920000915 polyvinyl chloride Polymers 0.000 description 33
- 235000016804 zinc Nutrition 0.000 description 17
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 11
- 239000013078 crystal Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000010583 slow cooling Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- SHLNMHIRQGRGOL-UHFFFAOYSA-N barium zinc Chemical compound [Zn].[Ba] SHLNMHIRQGRGOL-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 230000000069 prophylactic effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 2
- 229940007718 zinc hydroxide Drugs 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 125000006414 CCl Chemical group ClC* 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- FSFLVLNYYYJKRB-UHFFFAOYSA-N barium;methanol Chemical compound [Ba].OC FSFLVLNYYYJKRB-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- NYGZKMXIYAFNRM-UHFFFAOYSA-N methanol;zinc Chemical compound [Zn].OC NYGZKMXIYAFNRM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the organic barium of a kind of beta diketone class/zinc PVC heat stabilizer and preparation method thereof, belong to PVC heat stabilizer technical field.Technical scheme main points are：A kind of organic barium of beta diketone class/zinc PVC heat stabilizer, is that the organic barium compound of beta diketone class and beta diketone class organic zinc compound are added in dichloromethane, and cooling crystallization obtains after heating for dissolving, and the structural formula of the wherein organic barium compound of beta diketone class is, the structural formula of beta diketone class organic zinc compound is
Description
Technical field
The invention belongs to PVC heat stabilizer technical field, and in particular to a kind of organic barium of beta-diketon class/zinc PVC thermostabilizations
Agent and preparation method thereof.
Background technology
Polyvinyl chloride（Abbreviation PVC）It is one of five big general-purpose plastics, with its cheap price and very prominent harmony
Can and turn into very good material, and ancient and active kind, its global yield are only second to gather plastic applications in history
Ethene occupies second.China is one of big producer of polyvinyl chloride resin, and domestic PVC industry took by the development of more than 50 years
Rapid progress, the current country possess family more than 100 of Production of PVC enterprise, production capacity occupy first in synthetic resin at home
Position.
When general PVC is generally heated to more than 130 DEG C, just start to discharge HCl, because in manufacture PVC process
In, because Auto-oxidation reaction, chain termination reaction and the copolyreaction of micro amount of oxygen and some not yet clear and definite side reactions generate
Unstable C-Cl keys, and then HCl is discharged by thermal decomposition, and HCl can play catalytic action to the PVC decomposition that continues, and make
PVC is finally converted to containing undersaturated conjugated double bond structures（Polyenoid sequence）, such consecutive reaction, finally resulted in big point
Occurs long polyenoid sequence in subchain, when the double key number on macromolecular chain is more than 6, PVC will change colour.
Therefore, the heat stabilizer as PVC should possess prophylactic function and passivation.Wherein prophylactic function includes two sides
Face, on the one hand it is to absorb the HCl that PVC thermal degradations discharge, is on the other hand to eliminate the unstable chlorine atoms of PVC, so as to prevent
HCl generation；Passivation is the material of PVC performances of eliminating the effects of the act, and its method is that heat stabilizer enters with polyenoid sequence compound
Row addition reaction, long polyenoid sequence compound is set to shorten（Reduce conjugated double bond number）.At present, in the market is usually used in transparent modeling
The stabilizer of material production is liquid composition metal soaps stabilizer, such as barium zinc stabilizer, because its production with application process without powder
Dustiness dye, clean environment firendly and cheap, have obtained more and more extensive application.Liquid barium zinc stabilizer be barium zinc organic salt,
The compound of the components such as phosphite ester, polyalcohol, antioxidant and solvent.Liquid barium zinc stabilizer and resin and plasticizer intermiscibility
It is good, the transparency is good, be not easy to separate out, dosage is less and easy to use, major defect is that lubricity is poor, reduces the softening of product
Point, long-term storage can go bad.
Beta-diketone compounds are a kind of light stabilizers and heat stabilizer of important thermoplastic, are widely used in
In PVC plastic and ABS resin, be mainly used as polrvinyl chloride product helps heat stabilizer.As novel PVC auxiliary heat stabilizer,
Beta-diketone compounds have the advantages that efficient, nontoxic and multi-functional.With the heat stabilizer such as solid or liquid calcium/zinc, barium/zinc simultaneously
With precipitation and " zinc burning " in PVC initial colorations, transparency, long-time stability and process etc. can be substantially improved, extensively
For the nontoxic transparent PVC product such as medical treatment, packaging for foodstuff.All allow to use in food packaging applications in developed countries such as America and Europes
The product.
The content of the invention
Present invention solves the technical problem that there is provided, one kind can integrate barium/zinc stabilizer and beta-diketon class auxiliary is stable
The advantages of agent, make the organic barium of PVC thermostable effects more preferably beta-diketon class/zinc PVC heat stabilizer.
Another technical problem that the present invention solves there is provided one kind, and operation is simple, raw material is cheap and easy to get, reaction
The preparation method of the organic barium of the higher and reproducible beta-diketon class of efficiency/zinc PVC heat stabilizer.
The present invention adopts the following technical scheme that a kind of organic barium of beta-diketon class/zinc PVC heat is steady to solve above-mentioned technical problem
Determine agent, it is characterised in that be that the organic barium compound of beta-diketon class and beta-diketon class organic zinc compound are added to dichloromethane
In, cooling crystallization obtains after heating for dissolving, and the structural formula of the wherein organic barium compound of beta-diketon class is,
The structural formula of beta-diketon class organic zinc compound is, R is phenyl.
Further preferably, the specific building-up process of the described organic barium compound of beta-diketon class is：Filled to stirring is provided with
Nitrogen is passed through in the ultrasonic response container put, then adds dichloromethane solution and ammoniacal liquor dissolved with beta-diketone compounds,
Under 0-50 DEG C of reaction temperature into ultrasonic response container be added dropwise barium salt methanol solution, wherein beta-diketone compounds with
The molar ratio of barium salt is 1-2:1, agitating device and ultrasonic generator, ultrasonic generator are opened during dropwise addition
Setpoint frequency be 60-80KHz, after dripping stop stirring, keep ultrasonic generator work on, after being cooled to 0 DEG C
The steam vent on ultrasonic response container is opened, keeps the nitrogen that is passed through up to reaction solution crystallization is complete, to be taken out from steam vent discharge
Reaction solution is filtered, filter cake is washed repeatedly to wash away unnecessary barium salt with methanol, and filter cake obtains beta-diketon class after drying at room temperature have
Machine barium compound.
Further preferably, described reaction temperature is 25 DEG C, and the molar ratio of beta-diketone compounds and barium salt is 1:
1。
Further preferably, described barium salt is barium chloride.
Further preferably, the specific building-up process of described beta-diketon class organic zinc compound is：Filled to stirring is provided with
Nitrogen is passed through in the ultrasonic response container put, then adds dichloromethane solution and ammoniacal liquor dissolved with beta-diketone compounds,
Under 0-50 DEG C of reaction temperature into ultrasonic response container be added dropwise zinc salt methanol solution, wherein beta-diketone compounds with
The molar ratio of zinc salt is 1-2:1, agitating device and ultrasonic generator, ultrasonic generator are opened during dropwise addition
Setpoint frequency be 60-80KHz, after dripping stop stirring, keep ultrasonic generator work on, after being cooled to 0 DEG C
The steam vent on ultrasonic response container is opened, keeps the nitrogen that is passed through up to reaction solution crystallization is complete, to be taken out from steam vent discharge
Reaction solution is filtered, filter cake is washed repeatedly to wash away unnecessary zinc salt with methanol, and filter cake obtains beta-diketon class after drying at room temperature have
Machine zinc compound.
Further preferably, described reaction temperature is 25 DEG C, and the molar ratio of beta-diketone compounds and zinc salt is 1:
1。
Further preferably, described zinc salt is zinc chloride, zinc sulfate, zinc nitrate, zinc oxide or zinc hydroxide.
The preparation method of the organic barium of beta-diketon class/zinc PVC heat stabilizer of the present invention, it is characterised in that specific steps
For：By the organic barium compound of beta-diketon class and beta-diketon class organic zinc compound with 2:1 molar ratio is added to dichloromethane
In alkane, cooling crystallization obtains the organic barium of beta-diketon class/zinc PVC heat stabilizer after heating for dissolving.
The present invention has the advantages that compared with prior art：
1st, the organic barium of beta-diketon class/zinc PVC heat stabilizer of the invention combines barium/zinc stabilizer and beta-diketon class chemical combination
The advantage of thing auxiliary heat stabilizer, reach while more convenient using the effect of two kinds of materials, use；
2nd, in the preparation method of the organic barium compound of beta-diketon class of the invention and beta-diketon class organic zinc compound, use
The miscellaneous quality for influenceing product in the product of ammonium chloride bag that ultrasonic wave can effectively avoid reaction from generating, using nitrogen with whole
Reaction, under the conditions of 0 DEG C, solvent is not volatile, is volatilized by nitrogen with solvent, can not only promote crystallization, and can
Avoid oxygen from influenceing beta-diketone compounds to be combined with barium ions or zinc ion.
Embodiment
The above of the present invention is described in further details by the following examples, but this should not be interpreted as to this
The scope for inventing above-mentioned theme is only limitted to following embodiment, and all technologies realized based on the above of the present invention belong to this hair
Bright scope.
Embodiment 1
Nitrogen is passed through into the ultrasonic response container for being provided with agitating device, is then added dissolved with 1,3- diphenyl -1,
3- propanedione 22.5g（0.1mol）Dichloromethane solution 300mL, after adding ammoniacal liquor 100mL, under 50 DEG C of reaction temperature to
It is slowly added dropwise in ultrasonic response container dissolved with barium chloride 10g（0.05mol）Methanol solution 300mL, opened during dropwise addition
Agitating device and ultrasonic generator, the setpoint frequency of ultrasonic generator is 80KHz, and after dripping, solution is now
Clear state, stop stirring, keep ultrasonic generator to work on, for slow cooling to 0 DEG C, reaction solution is static, opens super
Steam vent on sound wave reaction vessel, the nitrogen for keeping being passed through are discharged from steam vent, make nitrogen with a certain amount of reaction dissolvent
Ultrasonic response container is discharged, gradually has colourless or light yellow crystal to separate out, crystallization is complete after 5h, filters reaction solution, and filter cake is used
Methanol is washed repeatedly to wash away unnecessary barium salt, and filter cake obtains 1,3- diphenyl -1,3- propanedione after drying at room temperature organic
Barium compound 15g.
Embodiment 2
Nitrogen is passed through into the ultrasonic response container for being provided with agitating device, is then added dissolved with 1,3- diphenyl -1,
3- propanedione 22.5g（0.1mol）Dichloromethane solution 300mL, after adding ammoniacal liquor 100mL, under 25 DEG C of reaction temperature to
It is slowly added dropwise in ultrasonic response container dissolved with barium chloride 20g（0.1mol）Methanol solution 300mL, during dropwise addition open stir
Device and ultrasonic generator are mixed, the setpoint frequency of ultrasonic generator is 80KHz, and after dripping, solution is now to be clear
Clear state, stop stirring, keep ultrasonic generator to work on, for slow cooling to 0 DEG C, reaction solution is static, opens ultrasound
Steam vent on ripple reaction vessel, the nitrogen for keeping being passed through are discharged from steam vent, nitrogen is arranged with a certain amount of reaction dissolvent
Go out ultrasonic wave reaction vessel, gradually there is colourless or light yellow crystal to separate out, crystallization is complete after 5h, filters reaction solution, filter cake first
Alcohol is washed repeatedly to wash away unnecessary barium salt, and filter cake obtains the organic barium of 1,3- diphenyl -1,3- propanedione after drying at room temperature
Compound 21g.
Embodiment 3
Nitrogen is passed through into the ultrasonic response container for being provided with agitating device, is then added dissolved with 1,3- diphenyl -1,
3- propanedione 22.5g（0.1mol）Dichloromethane solution 300mL, after adding ammoniacal liquor 100mL, under 25 DEG C of reaction temperature to
It is slowly added dropwise in ultrasonic response container dissolved with zinc chloride 14g（0.1mol）Methanol solution 300mL, during dropwise addition open stir
Device and ultrasonic generator are mixed, the setpoint frequency of ultrasonic generator is 60KHz, and after dripping, solution is now to be clear
Clear state, stop stirring, keep ultrasonic generator to work on, for slow cooling to 0 DEG C, reaction solution is static, opens ultrasound
Steam vent on ripple reaction vessel, the nitrogen for keeping being passed through are discharged from steam vent, nitrogen is arranged with a certain amount of reaction dissolvent
Go out ultrasonic wave reaction vessel, gradually there is colourless or light yellow crystal to separate out, crystallization is complete after 5h, filters reaction solution, filter cake first
Alcohol is washed repeatedly to wash away unnecessary zinc salt, and filter cake obtains 1,3- diphenyl -1,3- propanedione organic zincs after drying at room temperature
Compound 23g.
Embodiment 4
Nitrogen is passed through into the ultrasonic response container for being provided with agitating device, is then added dissolved with 1,3- diphenyl -1,
3- propanedione 22.5g（0.1mol）Dichloromethane solution 300mL, after adding ammoniacal liquor 100mL, under 0 DEG C of reaction temperature to
It is slowly added dropwise in ultrasonic response container dissolved with zinc hydroxide 10g（0.1mol）Methanol solution 300mL, opened during dropwise addition
Agitating device and ultrasonic generator, the setpoint frequency of ultrasonic generator is 60KHz, and after dripping, solution is now
Clear state, stop stirring, keep ultrasonic generator to work on, for slow cooling to 0 DEG C, reaction solution is static, opens super
Steam vent on sound wave reaction vessel, the nitrogen for keeping being passed through are discharged from steam vent, make nitrogen with a certain amount of reaction dissolvent
Ultrasonic response container is discharged, gradually has colourless or light yellow crystal to separate out, crystallization is complete after 5h, filters reaction solution, and filter cake is used
Methanol is washed repeatedly to wash away unnecessary zinc salt, and filter cake obtains 1,3- diphenyl -1,3- propanedione after drying at room temperature organic
Zinc compound 19g.
Embodiment 5
Nitrogen is passed through into the ultrasonic response container for being provided with agitating device, is then added dissolved with 1,3- diphenyl -1,
3- propanedione 22.5g（0.1mol）Dichloromethane solution 300mL, after adding ammoniacal liquor 100mL, under 50 DEG C of reaction temperature to
It is slowly added dropwise in ultrasonic response container dissolved with zinc oxide 8g（0.1mol）Methanol solution 300mL, during dropwise addition open stir
Device and ultrasonic generator are mixed, the setpoint frequency of ultrasonic generator is 60KHz, and after dripping, solution is now to be clear
Clear state, stop stirring, keep ultrasonic generator to work on, for slow cooling to 0 DEG C, reaction solution is static, opens ultrasound
Steam vent on ripple reaction vessel, the nitrogen for keeping being passed through are discharged from steam vent, nitrogen is arranged with a certain amount of reaction dissolvent
Go out ultrasonic wave reaction vessel, gradually there is colourless or light yellow crystal to separate out, crystallization is complete after 5h, filters reaction solution, filter cake first
Alcohol is washed repeatedly to wash away unnecessary zinc salt, and filter cake obtains 1,3- diphenyl -1,3- propanedione organic zincs after drying at room temperature
Compound 23g.
Embodiment 6
The organic barium compound 11.6g of 1,3- diphenyl -1,3- propanedione is added in reaction bulb（0.02mol）With 1,3- bis-
Diphenylpropane-1,3-dione (DPPO) organic zinc compound 5.1g（0.01mol）, dichloromethane 100mL is added, being heated to backflow makes its complete
Fully dissolved, 0 DEG C is cooled to after filtering while hot, reaction solution is static, opens the steam vent on ultrasonic response container, keeps what is be passed through
Nitrogen is discharged from steam vent, nitrogen is discharged ultrasonic response container with a certain amount of reaction dissolvent, gradually has colourless or light
Yellow crystals are separated out, and crystallization is complete after 5h, filter reaction solution, and filter cake is washed repeatedly with methanol, and filter cake obtains after drying at room temperature
To the organic barium of beta-diketon class/zinc PVC heat stabilizer 14g.
Embodiment 7
Heat stability testing
PVC material formula needed for detection, which forms, is：The plasticizer neighbour benzene two of the PVC material of 100 parts by weight, 5 parts by weight
Formic acid dioctyl ester, the titanium dioxide of 3 parts by weight and a certain amount of stabilizer, plasticate under the conditions of 180 DEG C in twin-screw extruder
To discoloration, the length for the time undergone during color change is observed（Time is longer, and explanation stabilizer effect is better）, it is above-mentioned each
Heat stabilizer addition used in part PVC material is as shown in the table.
As can be seen from the above table, the organic barium of beta-diketon class/zinc PVC heat stabilizer action effect obtained by the present invention exceedes
Traditional lead compound stabilizer, calcium-zinc composite stabilizing agent and organic tin stabilizer are horizontal.
Embodiment above describes the general principle of the present invention, main features and advantages, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, the original for simply illustrating the present invention described in above-described embodiment and specification
Reason, under the scope for not departing from the principle of the invention, various changes and modifications of the present invention are possible, and these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (7)
1. a kind of organic barium of beta-diketon class/zinc PVC heat stabilizer, is that the organic barium compound of beta-diketon class and beta-diketon class is organic
Zinc compound is added in dichloromethane, and cooling crystallization obtains after heating for dissolving, wherein beta-diketon class organic barium compound
Structural formula is, the structural formula of beta-diketon class organic zinc compound is, R is benzene
Base, it is characterised in that the specific building-up process of the described organic barium compound of beta-diketon class is：To being provided with the super of agitating device
Nitrogen is passed through in sound wave reaction vessel, dichloromethane solution and ammoniacal liquor dissolved with beta-diketone compounds are then added, in 0-50
DEG C reaction temperature under the methanol solution of barium salt, wherein beta-diketone compounds and barium salt are added dropwise into ultrasonic response container
Molar ratio is 1-2:1, agitating device and ultrasonic generator, the setting of ultrasonic generator are opened during dropwise addition
Frequency is 60-80KHz, stops stirring after dripping, and keeps ultrasonic generator to work on, and is opened after being cooled to 0 DEG C super
Steam vent on sound wave reaction vessel, from steam vent discharge up to reaction solution crystallization is complete, suction filtration reacts the nitrogen for keeping being passed through
Liquid, filter cake are washed repeatedly to wash away unnecessary barium salt with methanol, and filter cake obtains the organic barium of beta-diketon class after drying at room temperature
Compound.
2. the organic barium of beta-diketon class/zinc PVC heat stabilizer according to claim 1, it is characterised in that：Described reaction temperature
Spend for 25 DEG C, the molar ratio of beta-diketone compounds and barium salt is 1:1.
3. the organic barium of beta-diketon class/zinc PVC heat stabilizer according to claim 1, it is characterised in that：Described barium salt is
Barium chloride.
4. the organic barium of beta-diketon class/zinc PVC heat stabilizer according to claim 1, it is characterised in that described beta-diketon
The specific building-up process of class organic zinc compound is：Nitrogen is passed through into the ultrasonic response container for being provided with agitating device, so
The dichloromethane solution and ammoniacal liquor dissolved with beta-diketone compounds are added afterwards, to ultrasonic response under 0-50 DEG C of reaction temperature
The methanol solution of zinc salt is added dropwise in container, the wherein molar ratio of beta-diketone compounds and zinc salt is 1-2:1, process is added dropwise
Middle unlatching agitating device and ultrasonic generator, the setpoint frequency of ultrasonic generator is 60-80KHz, is stopped after dripping
Only stir, keep ultrasonic generator to work on, be cooled to the steam vent opened after 0 DEG C on ultrasonic response container, protect
The nitrogen being passed through is held from steam vent discharge up to reaction solution crystallization is complete, suction filtration reaction solution, filter cake is washed repeatedly with methanol to wash
Unnecessary zinc salt, filter cake is gone to obtain beta-diketon class organic zinc compound after drying at room temperature.
5. the organic barium of beta-diketon class/zinc PVC heat stabilizer according to claim 4, it is characterised in that：Described reaction temperature
Spend for 25 DEG C, the molar ratio of beta-diketone compounds and zinc salt is 1:1.
6. the organic barium of beta-diketon class/zinc PVC heat stabilizer according to claim 4, it is characterised in that：Described zinc salt is
Zinc chloride, zinc sulfate, zinc nitrate or zinc acetate.
A kind of 7. preparation method of the organic barium of beta-diketon class/zinc PVC heat stabilizer described in claim 1, it is characterised in that tool
Body step is：By the organic barium compound of beta-diketon class and beta-diketon class organic zinc compound with 2:1 molar ratio is added to
In dichloromethane, cooling crystallization obtains the organic barium of beta-diketon class/zinc PVC heat stabilizer after heating for dissolving.
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| US4116907A (en) * | 1976-08-02 | 1978-09-26 | Sekisui Kagaku Kogyo Kabushiki Kaisha | Chlorine-containing resin compositions |
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