CN106280066A - Mesoporous TiO 2 auxiliary PVC heat stabilizer and preparation method thereof - Google Patents
Mesoporous TiO 2 auxiliary PVC heat stabilizer and preparation method thereof Download PDFInfo
- Publication number
- CN106280066A CN106280066A CN201510308965.1A CN201510308965A CN106280066A CN 106280066 A CN106280066 A CN 106280066A CN 201510308965 A CN201510308965 A CN 201510308965A CN 106280066 A CN106280066 A CN 106280066A
- Authority
- CN
- China
- Prior art keywords
- mesoporous tio
- heat stabilizer
- stabilizer
- auxiliary
- pvc heat
- 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.)
- Pending
Links
Abstract
The present invention relates to a kind of mesoporous TiO 2 auxiliary PVC heat stabilizer and preparation method thereof, this heat stabilizer is made up of metallic soap main stabilizer and phosphite ester or the auxiliary stabilizer of epoxide, mesoporous TiO 2, antioxidant, lubricant, fire retardant.The present invention introduces mesoporous TiO 2 in PVC heat stabilizer, and the super big hole volume of mesoporous TiO 2 and specific surface area make it have the biggest adsorption capacity, reduces PVC and adds the HCL concentration in man-hour, is prevented effectively from or alleviates the further degraded of PVC；And the main stabilizers such as metallic soap and the co-stabilizer such as phosphite ester, epoxide can be made to be enriched with in mesoporous TiO 2 duct with HCL, so that stabilizer faster, preferably play a role, thus can significantly improve the thermostable effect of stabilizer simultaneously.
Description
Technical field
The present invention relates to a kind of PVC heat stabilizer, particularly to a kind of mesoporous TiO 2 auxiliary PVC heat stabilizer and preparation thereof
Method.
Background technology
Polrvinyl chloride (PVC) is the second largest synthetic resin being only second to polyethylene, is widely used in building, telecommunication, traffic, electricity
The industries such as son, chemical industry, packaging.But PVC poor heat stability, must be added to a certain amount of heat stabilizer to carry in the course of processing
Its heat stability high.Conventional heat stabilizer has lead salt, metal soap, organic tin, terres rares etc..Metal soap is thermally-stabilised
Agent is the second largest class main stabilizer that consumption is only second to lead salt.
According to metallic soap activity in stoping PVC degraded, metallic soap can be divided into two classes: a class is only capable of absorbing hydrogen chloride, anti-
Only its catalytic action to dehydrochlorination reaction, the most representational is barium soap and calcium soap.This kind of metallic soap heat stability is general,
Primary stability is bad, but is heated for a long time, and PVC stability change is little.The chloride generated in its stabilization procedures is to dechlorination
Change hydrogen-based this nothing catalytic action.Another kind of can not only absorbing hydrogen chloride, additionally it is possible to react so that PVC is stable with allyl chloride,
Most represent is cadmium soap and zinc soap.This kind of metallic soap initial coloring is fine, but long-term by hot article drastically variable color.Especially
, easily there is drastically melanism in zinc soap, produces so-called " zinc burning " phenomenon.It is used alone any kind metallic soap, is all extremely difficult to
Satisfied stablizing effect.If by cadmium high for activity, zinc soap and the barium of poor activity, calcium use, then initial coloring and length can be made
Phase stability is all improved.
The features such as homogeneous, the narrow ditribution in super big hole surface area, pore volume and aperture that mesoporous TiO 2 has so that it is in preparation
During the heat stabilizer of function admirable, there is advantage.
Summary of the invention
It is an object of the invention to: the mesoporous TiO 2 providing a kind of stability more excellent assists PVC heat stabilizer and preparation method thereof.
The technical scheme realizing the object of the invention is: a kind of mesoporous TiO 2 auxiliary PVC heat stabilizer, this heat stabilizer is by gold
Belong to soap main stabilizer and phosphite ester or the auxiliary stabilizer of epoxide, mesoporous TiO 2, antioxidant, lubricant, fire-retardant
Agent forms.
Mesoporous TiO 2 of the present invention auxiliary PVC heat stabilizer, described mesoporous TiO 2 addition is total formula
5～10wt%, preferably 5.5wt%, 6wt%, 6.5wt%, 7wt%, 7.5wt%, 8wt%, 8.5wt%, 9wt%, 9.5
Wt%, 10wt%.
Mesoporous TiO 2 of the present invention auxiliary PVC heat stabilizer, each constituent mass percentage ratio is:
Above-mentioned mesoporous TiO 2 auxiliary PVC heat stabilizer, described antioxidant be three (2,4-di-tert-butyl-phenyl) phosphite ester,
Four (2,4-di-t-butyl eight alkoxyl-4,4-xenyl) phosphate ester, double (2,4-di-tert-butyl-phenyl) tetramethylolmethane diphosphorous acid
Ester, (2,4,6-tri-tert phenyl-2-butyl-2-ethyl)-1,3-diol phosphite, four (2,4-di-tert-butyl-phenyl-4,4 '
-xenyl) biphosphonate, Distearyl pentaerythritol, trisnonylphenyl phosphite, diphosphorous acid two (ten
One of tetrol) pentaerythritol ester.
Above-mentioned mesoporous TiO 2 auxiliary PVC heat stabilizer, described lubricant is neck phthalic acid glycerol two stearic acid ester, ten
One of eight alkanols, 18 fatty acids, paraffin, Tissuemat E, amide waxe.
Above-mentioned mesoporous TiO 2 auxiliary PVC heat stabilizer, described fire retardant be magnesium hydroxide, aluminium hydroxide, zinc it
One.
Phosphite ester be phosphorous acid benzene Diisooctyl, phosphorous acid benzene didecyl, triphenyl phosphite, phosphorous acid hexichol isodecyl ester it
One.
Mesoporous TiO 2 of the present invention auxiliary PVC heat stabilizer, described each constituent mass percentage ratio is preferably:
Mesoporous TiO 2 of the present invention auxiliary PVC heat stabilizer, described each constituent mass percentage ratio is more preferably:
Mesoporous TiO 2 of the present invention auxiliary PVC heat stabilizer, described each constituent mass percentage ratio is more preferably:
Mesoporous TiO 2 of the present invention auxiliary PVC heat stabilizer, described each constituent mass percentage ratio is more preferably:
The preparation method of mesoporous TiO 2 of the present invention auxiliary PVC heat stabilizer, comprises the steps:
(1) zinc stearate, calcium stearate, phosphite ester are put in reaction vessel, be heated with stirring to 65～85 DEG C, add
Mesoporous TiO 2 is warming up to 95～105 DEG C again, stirs 20～30min；
(2), before again antioxidant, lubricant, fire retardant being added in step reactant liquor, it is slowly stirred, and is warming up to 110～120 DEG C,
Keep 30～60min, be then filtrated to get mesoporous TiO 2 auxiliary PVC heat stabilizer.
The features such as super big hole surface area that mesoporous TiO 2 has, the homogeneous narrow ditribution of pore volume and aperture so that it is in preparative
Can have the advantage that the super big hole volume of mesoporous TiO 2 and specific surface area make it have the biggest absorption during excellent heat stabilizer
Capacity, not only can be substantially reduced PVC by self absorption HCL and add the HCL concentration in man-hour, be prevented effectively from or subtract entering of PVC
One step degraded；And the main stabilizers such as metallic soap and the co-stabilizer such as phosphite ester, epoxide can be made to exist with HCL simultaneously
Mesoporous TiO 2 duct is enriched with, so that stabilizer faster, preferably play a role, thus can significantly improve stabilizer
Thermostable effect；Additionally, with great amount of hydroxy group in mesoporous TiO 2 surface and pore passage structure, can be with phosphite ester and diketone
Compounds produces good synergism, significantly improves the stability of stabilizer.
The present invention has positive effect: the present invention introduces mesoporous TiO 2 in PVC heat stabilizer, mesoporous TiO 2
Super big hole volume and specific surface area make it have the biggest adsorption capacity, reduce PVC and add the HCL concentration in man-hour, be prevented effectively from or
Alleviate the further degraded of PVC；And the main stabilizers such as metallic soap and the co-stabilizer such as phosphite ester, epoxide can be made
It is enriched with in mesoporous TiO 2 duct with HCL, so that stabilizer can be faster, preferably play a role thus aobvious simultaneously
Write the thermostable effect improving stabilizer.
Detailed description of the invention
(embodiment 1) weigh zinc stearate 25.5Kg, calcium stearate 43.5Kg, phosphorous acid benzene didecyl 12.5Kg, mesoporous two
Titanium oxide 6.5Kg, three (2,4-di-tert-butyl-phenyl) phosphite ester 2.4Kg, neck phthalic acid glycerol two stearic acid ester 4.6Kg,
Magnesium hydroxide 3.5Kg.
Then it is prepared as follows:
(1) zinc stearate, calcium stearate, phosphorous acid benzene didecyl are put in reaction vessel, be heated with stirring to 68 DEG C, add
Mesoporous TiO 2 is warming up to 96 DEG C again, stirs 20min；
(2) again by antioxidant three (2,4-di-tert-butyl-phenyl) phosphite ester, lubricant neck phthalic acid glycerol two stearic acid ester,
Fire retardant magnesium hydroxide walks in reactant liquor before adding, and is slowly stirred, and is warming up to 110 DEG C, keeps 30min, is then filtrated to get
Mesoporous TiO 2 auxiliary PVC heat stabilizer.
PVC heat stabilizer prepared by polyvinyl chloride resin, the present embodiment, addition is 0.7wt% and after other auxiliary agent mixed at high speed,
In two-roll mill mixing after, plasticizing, bottom sheet, section, be cut into the small pieces of 5mm*5mm, obtain PVC style, survey
Examination.
(embodiment 2) weighs zinc stearate 53Kg, calcium stearate 16.6Kg, triphenyl phosphite 10.5Kg, mesoporous dioxy
Change titanium 7.5Kg, four (2,4-di-t-butyl eight alkoxyl-4,4-xenyl) phosphate ester 1.1Kg, octadecanol 5.6Kg, hydrogen-oxygen
Change aluminum 4.3Kg.
Then it is prepared as follows:
(1) zinc stearate, calcium stearate, triphenyl phosphite are put in reaction vessel, be heated with stirring to 70 DEG C, add and be situated between
Porous titanium dioxide is warming up to 98 DEG C again, stirs 30min；
(2) again by antioxidant four (2,4-di-t-butyl eight alkoxyl-4,4-xenyl) phosphate ester, lubricant octadecanol, resistance
Combustion agent aluminium hydroxide walks in reactant liquor before adding, and is slowly stirred, and is warming up to 110 DEG C, keeps 30min, is then filtrated to get Jie
Porous titanium dioxide auxiliary PVC heat stabilizer.
PVC heat stabilizer prepared by polyvinyl chloride resin, the present embodiment, addition is 0.7wt% and after other auxiliary agent mixed at high speed,
In two-roll mill mixing after, plasticizing, bottom sheet, section, be cut into the small pieces of 5mm*5mm, obtain PVC style, survey
Examination.
(embodiment 3) weigh zinc stearate 32Kg, calcium stearate 33.5Kg, phosphorous acid hexichol isodecyl ester 10Kg, mesoporous two
Titanium oxide 9.5Kg, double (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites 2.5Kg, Tissuemat E 6.0Kg, stannic acid
Zinc 5.0Kg.
Then it is prepared as follows:
(1) zinc stearate, calcium stearate, phosphorous acid hexichol isodecyl ester are put in reaction vessel, be heated with stirring to 70 DEG C, add
Enter mesoporous TiO 2 and be warming up to 98 DEG C again, stir 30min；
(2) again by double for antioxidant (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, lubricant polyethylene wax, fire-retardant
Agent zinc walks in reactant liquor before adding, and is slowly stirred, and is warming up to 110 DEG C, keeps 30min, is then filtrated to get mesoporous two
Titanium oxide auxiliary PVC heat stabilizer.
PVC heat stabilizer prepared by polyvinyl chloride resin, the present embodiment, addition is 0.7wt% and after other auxiliary agent mixed at high speed,
In two-roll mill mixing after, plasticizing, bottom sheet, section, be cut into the small pieces of 5mm*5mm, obtain PVC style, survey
Examination.
(embodiment 4) weighs zinc stearate 13Kg, calcium stearate 52.5Kg, phosphorous acid hexichol isodecyl ester 14.5Kg, mesoporous
Titanium dioxide 4.5Kg, double (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites 1.5Kg, Tissuemat E 7.5Kg, stannum
Acid zinc 4.0Kg.
Then it is prepared as follows:
(1) zinc stearate, calcium stearate, phosphorous acid hexichol isodecyl ester are put in reaction vessel, be heated with stirring to 70 DEG C, add
Enter mesoporous TiO 2 and be warming up to 98 DEG C again, stir 30min；
(2) again by double for antioxidant (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, lubricant polyethylene wax, fire-retardant
Agent zinc walks in reactant liquor before adding, and is slowly stirred, and is warming up to 110 DEG C, keeps 30min, is then filtrated to get mesoporous two
Titanium oxide auxiliary PVC heat stabilizer.
PVC heat stabilizer prepared by polyvinyl chloride resin, the present embodiment, addition is 0.7wt% and after other auxiliary agent mixed at high speed,
In two-roll mill mixing after, plasticizing, bottom sheet, section, be cut into the small pieces of 5mm*5mm, obtain PVC style, survey
Examination.
(embodiment 5) weighs zinc stearate 42Kg, calcium stearate 20.5Kg, phosphorous acid hexichol isodecyl ester 17.3Kg, mesoporous
Titanium dioxide 7.5Kg, double (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites 1.8Kg, Tissuemat E 4.7Kg, stannum
Acid zinc 4.3Kg.
Then it is prepared as follows:
(1) zinc stearate, calcium stearate, phosphorous acid hexichol isodecyl ester are put in reaction vessel, be heated with stirring to 70 DEG C, add
Enter mesoporous TiO 2 and be warming up to 98 DEG C again, stir 30min；
(2) again by double for antioxidant (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, lubricant polyethylene wax, fire-retardant
Agent zinc walks in reactant liquor before adding, and is slowly stirred, and is warming up to 110 DEG C, keeps 30min, is then filtrated to get mesoporous two
Titanium oxide auxiliary PVC heat stabilizer.
PVC heat stabilizer prepared by polyvinyl chloride resin, the present embodiment, addition is 0.7wt% and after other auxiliary agent mixed at high speed,
In two-roll mill mixing after, plasticizing, bottom sheet, section, be cut into the small pieces of 5mm*5mm, obtain PVC style, survey
Examination.
Particular embodiments described above, is further described the purpose of the present invention, technical scheme and beneficial effect,
Be it should be understood that the specific embodiment that the foregoing is only the present invention, be not limited to the present invention, all in the present invention
Spirit and principle within, any modification, equivalent substitution and improvement etc. done, should be included in protection scope of the present invention it
In.
Claims (8)
1. mesoporous TiO 2 auxiliary PVC heat stabilizer, it is characterised in that: this heat stabilizer by metallic soap main stabilizer,
Stabilizer auxiliary with phosphite ester or epoxide, mesoporous TiO 2, antioxidant, lubricant, fire retardant form.
Mesoporous TiO 2 the most according to claim 1 auxiliary PVC heat stabilizer, it is characterised in that: described mesoporous dioxy
Changing titanium addition is the 5～10wt% of total formula.
Mesoporous TiO 2 the most according to claim 1 and 2 auxiliary PVC heat stabilizer, it is characterised in that: each component matter
Amount percentage ratio is:
Mesoporous TiO 2 the most according to claim 3 auxiliary PVC heat stabilizer, it is characterised in that: described antioxidant is
Three (2,4-di-tert-butyl-phenyl) phosphite ester, four (2,4-di-t-butyl eight alkoxyl-4,4-xenyl) phosphate ester, double (2,4-
Di-tert-butyl-phenyl) pentaerythritol diphosphites, (2,4,6-tri-tert phenyl-2-butyl-2-ethyl)-1,3-propylene glycol phosphorous
Acid esters, four (2,4-di-tert-butyl-phenyl-4,4 '-xenyl) biphosphonate, Distearyl pentaerythritol, three nonyls
One of base phenyl phosphites, diphosphorous acid two (tetradecyl alchohol) pentaerythritol ester.
Mesoporous TiO 2 the most according to claim 3 auxiliary PVC heat stabilizer, it is characterised in that: described lubricant is
Neck one of phthalic acid glycerol two stearic acid ester, octadecanol, 18 fatty acids, paraffin, Tissuemat E, amide waxe.
Mesoporous TiO 2 the most according to claim 3 auxiliary PVC heat stabilizer, it is characterised in that: described fire retardant is
One of magnesium hydroxide, aluminium hydroxide, zinc.
Mesoporous TiO 2 the most according to claim 3 auxiliary PVC heat stabilizer, it is characterised in that described each constituent mass
Percentage ratio is:
8. a preparation method for the mesoporous TiO 2 auxiliary PVC heat stabilizer as described in as arbitrary in claim 1～7, it is special
Levy and be to comprise the steps:
(1) zinc stearate, calcium stearate, phosphite ester are put in reaction vessel, be heated with stirring to 75～95 DEG C, add
Mesoporous TiO 2 is warming up to 95～115 DEG C again, stirs 20～30min；
(2), before again antioxidant, lubricant, fire retardant being added in step reactant liquor, it is slowly stirred, and is warming up to 105～120 DEG C,
Keep 30～60min, be then filtrated to get mesoporous TiO 2 auxiliary PVC heat stabilizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510308965.1A CN106280066A (en) | 2015-06-08 | 2015-06-08 | Mesoporous TiO 2 auxiliary PVC heat stabilizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510308965.1A CN106280066A (en) | 2015-06-08 | 2015-06-08 | Mesoporous TiO 2 auxiliary PVC heat stabilizer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106280066A true CN106280066A (en) | 2017-01-04 |
Family
ID=57658701
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510308965.1A Pending CN106280066A (en) | 2015-06-08 | 2015-06-08 | Mesoporous TiO 2 auxiliary PVC heat stabilizer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106280066A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107118454A (en) * | 2017-04-10 | 2017-09-01 | 河源市鑫达科技有限公司 | PVC cable special-purpose anti-flaming heat endurance auxiliary agent and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102477196A (en) * | 2010-11-30 | 2012-05-30 | 山东慧科助剂股份有限公司 | Novel molecular sieve PVC composite stabilizing agent and its preparation method |
| CN102516686A (en) * | 2011-12-05 | 2012-06-27 | 山东慧科助剂股份有限公司 | Environmentally-friendly efficient composite heat stabilizer for nanometer beta molecular sieve-based PVC (Polyvinyl Chloride) and preparation method thereof |
| CN102964744A (en) * | 2012-12-10 | 2013-03-13 | 山东慧科助剂股份有限公司 | Thermal stabilizer for aluminate modified molecular sieve PVC and preparation method thereof |
-
2015
- 2015-06-08 CN CN201510308965.1A patent/CN106280066A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102477196A (en) * | 2010-11-30 | 2012-05-30 | 山东慧科助剂股份有限公司 | Novel molecular sieve PVC composite stabilizing agent and its preparation method |
| CN102516686A (en) * | 2011-12-05 | 2012-06-27 | 山东慧科助剂股份有限公司 | Environmentally-friendly efficient composite heat stabilizer for nanometer beta molecular sieve-based PVC (Polyvinyl Chloride) and preparation method thereof |
| CN102964744A (en) * | 2012-12-10 | 2013-03-13 | 山东慧科助剂股份有限公司 | Thermal stabilizer for aluminate modified molecular sieve PVC and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107118454A (en) * | 2017-04-10 | 2017-09-01 | 河源市鑫达科技有限公司 | PVC cable special-purpose anti-flaming heat endurance auxiliary agent and preparation method thereof |
| CN107118454B (en) * | 2017-04-10 | 2020-05-12 | 河源市鑫达科技有限公司 | Special flame-retardant heat-stability auxiliary agent for PVC (polyvinyl chloride) wires and cables and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105121542B (en) | Opaque products vinyl chloride resin composition | |
| CN102898741B (en) | Polyvinyl chloride heat stabilizer and preparation method thereof | |
| CN107163443B (en) | Levulinic ketone rare earth complex heat stabilizer and its PVC material | |
| CN108084472B (en) | Hydrotalcite/phosphorus-nitrogen flame retardant compound flame-retardant PET material and preparation method thereof | |
| CN100480309C (en) | Composite stabilizer of metal salt of organic carboxylic acid containing sulfur in use for polymer containing halogen, and application thereof | |
| US20150353711A1 (en) | Pvc flame retardant compositions | |
| CN107099104B (en) | Magnalium hydrotalcite composite thermal stabilizer and preparation method thereof, application | |
| CN103833739A (en) | A calcium-zinc composite heat stabilizer, a preparation method thereof and applications thereof | |
| JP2015522691A5 (en) | ||
| CN104356565B (en) | A kind of aluminium phosphate molecular sieve fire retardant and preparation method thereof | |
| CN101939375B (en) | Flame-retardant chlorine-containing resin composition | |
| JP6266149B2 (en) | Liquid overbased carboxylic acid metal salt, mixed metal stabilizer containing the same, and method for preparing halogen-containing polymer stabilized by them | |
| CN105086234A (en) | Polyvinyl chloride single-wall corrugated pipe used for buildings and preparation method of polyvinyl chloride single-wall corrugated pipe | |
| WO2013004265A1 (en) | Surface covering comprising a citrate-based plasticizer | |
| CN104910447B (en) | A kind of flame retardant rubber | |
| CN101274994B (en) | Stabilizing agent compound for koroseal | |
| CN109593266A (en) | A kind of ultralow smoke density non-halogen flame-retardant cable and preparation method thereof | |
| CN106280066A (en) | Mesoporous TiO 2 auxiliary PVC heat stabilizer and preparation method thereof | |
| CN102504340A (en) | Nontoxic calcium and zinc thermal stabilizer | |
| CN105273337B (en) | PVC organic complex Zn composite heat stabilizers and preparation method thereof | |
| CN106280065A (en) | A kind of mesoporous silicon load P VC heat stabilizer and preparation method thereof | |
| CN105802436A (en) | Nano expanding type transparent fireproof paint and preparation method thereof | |
| CN103740038A (en) | High-glossiness halogen-free flame-retardant ABS material and preparation method thereof | |
| RU2012108753A (en) | ELECTRIC INSULATION POLYMER COMPOSITION | |
| CN103819832A (en) | Low-halogen flame retarding PVC (Polyvinyl Chloride) pipe material and preparing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170104 |