CN102515185A - Zinc hydroxystannate-palygorskite clay compound, its preparation and application as fire retardant - Google Patents
Zinc hydroxystannate-palygorskite clay compound, its preparation and application as fire retardant Download PDFInfo
- Publication number
- CN102515185A CN102515185A CN2011104047249A CN201110404724A CN102515185A CN 102515185 A CN102515185 A CN 102515185A CN 2011104047249 A CN2011104047249 A CN 2011104047249A CN 201110404724 A CN201110404724 A CN 201110404724A CN 102515185 A CN102515185 A CN 102515185A
- Authority
- CN
- China
- Prior art keywords
- palygorskite clay
- fire retardant
- hydroxyl stannate
- zinc hydroxyl
- preparation
- 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.)
- Granted
Links
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a zinc hydroxystannate-palygorskite clay compound which is prepared from raw materials of zinc chloride trihydrate, tin chloride and palygorskite clay by the adoption of a coprecipitation method. The compound has high flame retardancy and high smoke suppression, is used to prepare a flame-retardant polyvinyl chloride material, can replace present antimony series flame-retardation smoke suppressant to obtain a high-molecular material with good flame retardancy, smoke suppression and mechanical properties: oxygen index is not less than 34; horizontal burning reaches HB-a level; vertical burning reaches UL94V-0 level; smoke density under the flameless condition is low and is not greater than 286; tensile strength is more than 10.8 MPa and elongation at break is more than 210%. The zinc hydroxystannate-palygorskite clay compound completely satisfies B1 rule on building material combustion grade in GB/T8624-1997 and rules on each performance of wire and cable sheathed wire materials in the industry standard YD/T1113-2001.
Description
Technical field
The invention belongs to technical field of composite materials, relate to a kind of zinc hydroxyl stannate-palygorskite clay mixture; The invention still further relates to zinc hydroxyl stannate-palygorskite clay mixture as the application of fire retardant in the flame-proof polyvinyl chloride material.
?
Background technology
SE (PVC) material itself has noninflammability, HS, weather variability and good geometrical stability, and in addition, PVC has very strong resistibility to oxygenant, reductive agent and strong acid.Be mainly used in water supply line at present, home pipeline, house wallboard, business machine housing, electronic product packing, medicine equipment, electric wire crust, fields such as food product pack.
The beginning of this century; China has reached more than 80 ten thousand tons in the PVC product amount aspect tubing, the section bar, but needs a large amount of softening agent of adding in the PVC course of processing, inhibitor; Auxiliary agents such as lubricant; Cause the polrvinyl chloride product easy firing, it can discharge hydrogenchloride and other toxic gas ianthone such as dioxin in combustion processes), the difficulty that makes the people be difficult to take one's bearings and cause rescue and flee from the scene of a fire with the path.80% of death toll be to be choked to death in the fire according to statistics because of the toxic gas that when burning produces.Therefore, prepare fire-retardant low cigarette PVC material and have very important realistic meaning.
Flame-retardant smoke inhibition research to PVC at present mainly concentrates on following several fields: the first, in the PVC goods, directly add antimony series compound flame retardant (like Sb
2O
3) can reach good flame retardant effect, but since the price of antimony serial flame retardant constantly soaring with and the genotoxic potential that exists, will influence such additive in future market prospect; The second, add the inorganic hydroxide series material, like white lake, Marinco H etc. though such material is cheap, also need composite use, and flame retardant effect are undesirable; The 3rd; The zinc borate series additive; This series additive is the very good inorganic combustion inhibitor of a kind of performance, have fire-retardant, press down cigarette, promote into charcoal and prevent function such as molten drop, receive and pay close attention to widely and study; But at present zinc borate fire-retardant agent product in base material, disperses undesirable, the use properties of deterioration material during high addition; The 4th, other mineral-type additives are like molybdic oxide, clay mineral, MOX etc.
Summary of the invention
The present invention seeks to provides a kind of zinc hydroxyl stannate-palygorskite clay mixture to the problem that exists in the prior art.
Another object of the present invention provide a kind of with zinc hydroxyl stannate-palygorskite clay mixture as the application of main fire retardant in preparation flame-proof polyvinyl chloride matrix material.
One, zinc hydroxyl stannate-palygorskite clay mixture preparation
Zinc hydroxyl stannate of the present invention-palygorskite clay mixture is to be prepared from following process step: with ZnCl
23H
2O is soluble in water, adds ZnCl
23H
2The palygorskite clay that O (three hydration zinc chloride) quality is 5 ~ 20 times is heated to 80 ~ 95 ℃, stirs 20 ~ 40min; The pH of regulation system=5.0 ~ 6.4; Add ZnCl
23H
2The SnCl that O (three hydration zinc chloride) quality is 2 ~ 5 times
45H
2O stirs 10 ~ 25min; The final pH of conditioned reaction system=9.0 ~ 9.4, room temperature crystallization 3 ~ 5 h, filtering precipitate, washing, oven dry is ground, and obtains zinc hydroxyl stannate-palygorskite clay mixture.
Through infrared spectrum, XRD, transmission electron microscope, ESEM the structure of the zinc hydroxyl stannate-palygorskite clay mixture of the present invention's preparation is characterized and analyzes below.
Fig. 1,2 is respectively the infrared spectrogram of palygorskite clay, zinc hydroxyl stannate-palygorskite clay mixture.Comparison diagram 1,2 can be found out, zinc hydroxyl stannate of the present invention-palygorskite clay mixture is at 1170cm
-1The stretching vibration peak of Sn-O-H has appearred in the place, explains that zinc-palygorskite clay matrix material successfully prepares.
Fig. 3,4 is respectively the XRD curve (since 5 ° of-70 ° of curves that scan) of palygorskite clay, zinc hydroxyl stannate-palygorskite clay mixture.Through relatively finding out; The characteristic peak (2 θ=22.7) of characteristic peak of palygorskite clay (2 θ=8.4) and zinc hydroxyl stannate all occurs in zinc hydroxyl stannate-palygorskite clay mixture; Explanation does not destroy the crystalline structure of every kind of raw material using settling process to prepare in the process of fire retardant.
Fig. 5,6 is respectively the transmission electron microscope photo of palygorskite clay, zinc hydroxyl stannate-palygorskite clay mixture.Can find out from Fig. 5,6; Zinc hydroxyl stannate-palygorskite clay mixture is to have coated one deck zinc hydroxyl stannate on the palygorskite clay surface; But because the proportion relation of zinc and palygorskite clay, coating is not very complete, and this also is the result that we want before experiment; Because the palygorskite clay that exposes can be brought into play the effect of its flame-retardant smoke inhibition, thus and the collaborative fire retardation that plays of zinc.
Two, the preparation of flame-proof polyvinyl chloride matrix material
Flame-proof polyvinyl chloride matrix material of the present invention is to be fire retardant with zinc hydroxyl stannate-palygorskite clay mixture, is matrix with the SE, and the method through melting mixing makes.The addition of said fire retardant zinc hydroxyl stannate-palygorskite clay is 5 ~ 45% of a SE substrate quality.
In order to reduce cost; Alleviate the density of PVC material; Improve the mechanical property of PVC material; Assist fire retardant that the PVC matrix is reduced smoke density, in the preparation of flame retardant resistance polyvinyl chloride composite materials, 3 ~ 10% the cupric oxide powder of 5 ~ 15% wood powder (mainly being culled wood pulverised material such as pine tree wood powder, willow wood powder, elm wood powder, Chinese scholartree wood powder, cypress wood powder) and SE substrate quality that also can add the SE substrate quality is as filler.
In order to prevent that PVC in the course of processing from decomposing and improving the mechanical property of matrix material, in the preparation of flame retardant resistance polyvinyl chloride composite materials, the stablizer that also adds convention amount (comprises lead sulfate tribasic like the lead salts stablizer; Alkali property plumbous sulfite, dibasic lead phosphite, dibasicity O-phthalic lead plumbate; Tribasic Malaysia lead plumbate, lead stearate, dibasic lead stearate; Silica gel co-precipitation lead silicate, white lead etc.; The metallic soap class; Organic tin; Rare earth class; Complex class), (phthalic ester is like dioctyl terephthalate for softening agent; Fatty group dibasic acid is like Octyl adipate, dioctyl sebacate; SULPHOSUCCINIC ACID ESTER is like Tritolyl Phosphate, phosphate toluene diphenyl ester; Epoxy compounds is like epoxidised soybean oil, epoxyoleic acid butyl ester; Reoplex is like the hexanodioic acid Ucar 35; Benzene polyacid ester, as 1,2, the 4-triisooctyl trimellitate; Chloro-plasticizer is like clorafin, pentachloro-methyl stearate; Alkyl sulfonic ester; Polyol ester etc.).
In order to make the good fluidity of material in the course of processing, in the preparation of flame retardant resistance polyvinyl chloride composite materials, also added the lubricant (like whiteruss, Triple Pressed Stearic Acid etc.) of convention amount.
Structure, flame retardant properties and mechanical property in the face of the flame-proof polyvinyl chloride matrix material describes down.
Fig. 7 is the ESEM picture of flame-proof polyvinyl chloride matrix material.Can observe through Fig. 7, additive (comprising fire retardant and other fillers) is dispersed in the matrix with nano level, and with the SE matrix good consistency is arranged.
The test of flame-proof polyvinyl chloride matrix material composite property:
(1) flame retardant properties: according to the limiting oxygen index(LOI) of GB/ T 2406.2-2009 test sample; Horizontal vertical combustionproperty according to GB/ T 2408-2008 test sample.The result is following: oxygen index is not less than 34; Horizontal firing reaches the HB-a level, and vertical combustion reaches the UL94V-0 level.Satisfy fully among the GB/T 8624-1997 and reach B about structure material burning rank
1Regulation and YD/T 1113-2001 in stipulate about electric wire skin material incendiary.
(2) smoke density: according to the smoke density of GB/ T 8323.2-2008 test sample.Smoke density is lower than 286 under the nonflame condition.
(3) mechanical property: carry out the test of tensile strength and elongation at break according to GB1040; Test result is: tensile strength is all more than 10.8MPa; Elongation at break is all more than 210%, and material each item performance meets among the industry standard YD/T 1113-2001 regulation about electric wire foreskin material mechanical performance.
The structure of comprehensive composite flame-retardant agent and PVC is following to the flame-retardant smoke inhibition mechanism of PVC:
The first, the Zn in the zinc hydroxyl stannate
2+And Sn
4+Be strong lewis acid, ability catalysis PVC takes off HCl and generates trans polyene structure, and this transconfiguration can not cyclisation generate aromatic hydrocarbon, thereby has suppressed the further degraded of PVC main chain;
The second, Zn
2+And Sn
4+The ZnCl that can generate with the HCl that PVC discharges
2And SnCl
4It also is Lewis acid; Not only can further promote the crosslinked and carbonization reaction of intermolecular generation, in solid phase, promote to generate fine and close charring layer, play heat insulation, oxygen barrier effect; Stoped the PVC incendiary to be proceeded; Thereby improved neat coal amout, and absorbed, having reduced the amount of flue gas release and toxic gas through reaction to HCl gas;
The 3rd; Palygorskite clay begins to decompose at a certain temperature, produces a large amount of MOX and water vapour, bears heat insulation oxygen barrier effect with the charcoal layer that under the zinc hydroxyl stannate effect, generates; Reduce PVC pyrolysis or combustionmaterial surface temperature, cigarette in the minimizing process and toxic gas.After the pyrolysis thermo-negative reaction taking place and reduce the temperature in PVC pyrolysis or the burning situation, reduces the material combustion HRR.
The present invention is relative, and prior art has the following advantages:
1, the present invention is a raw material with three water zinc chloride, tin chloride and palygorskite clay, adopts coprecipitation method to prepare zinc hydroxyl stannate-palygorskite clay anti-flaming smoke-inhibiting agent, has opened up anti-flaming smoke-inhibiting agent and has not had the chlorination frontier.
2, fire retardant of the present invention is a raw material with palygorskite clay cheap and easy to get etc., and production technique is simple, and cost is low.
3, the zinc hydroxyl stannate-palygorskite clay fire retardant of the present invention's preparation has high flame resistance and high smoke suppressing; In preparation flame retardant resistance polymer composite; The anti-flaming smoke-inhibiting agent of the present antimony series of instead obtains the good macromolecular material of flame retardant properties and smoke suppressing.
Description of drawings
Fig. 1 is the palygorskite clay infrared spectrogram.
Fig. 2 is the infrared spectrogram of zinc hydroxyl stannate of the present invention-palygorskite clay mixture.
Fig. 3 is the XRD curve of palygorskite clay.
Fig. 4 coats palygorskite clay XRD curve for zinc hydroxyl stannate.
Fig. 5 is the palygorskite clay transmission electron microscope photo.
Fig. 6 is the transmission electron microscope photo of zinc hydroxyl stannate of the present invention-palygorskite clay mixture.
Fig. 7 is the ESEM in flame-proof polyvinyl chloride matrix material transverse section.
Embodiment
Through specific embodiment the preparation of fire retardant of the present invention and flame-proof polyvinyl chloride matrix material affected is gone on foot explanation below.
Embodiment 1
(1) preparation of fire retardant zinc hydroxyl stannate-palygorskite clay
ZnCl with 10 g
23H
2O is dissolved in the 100 ml zero(ppm) water, adds 50 g palygorskite clay (attapulgite), is heated to 80 ℃, stirs 20 min.With HCl regulation system pH=5.0; Add 20 g SnCl
45H
2O, violent stirring 10 min, with final pH=9.0 of NaOH conditioned reaction system, crystallization 3 h under the room temperature, filtering precipitate, washing is put into baking oven then and is dried, and grinds the 300m sieve, obtains zinc hydroxyl stannate-palygorskite clay fire retardant.
(2) preparation of flame-proof polyvinyl chloride matrix material
With 5 g zinc hydroxyl stannate-palygorskite clay; 5 g wood powders; 3 g cupric oxide powders, 1 g stablizer (lead sulfate tribasic), 5 g softening agent (phthalic ester), 0.5 g lubricant (whiteruss) add in the 100 g SE matrixes; Through the method for melting mixing, prepared the LSOH anti-flaming polyvinyl chloride composite materials.
Each item performance of matrix material: oxygen index is 34, and horizontal firing reaches the HB-a level, and vertical combustion reaches the UL94V-0 level, and smoke density is 270 under the nonflame condition, and tensile strength is 10.8 MPa, and elongation at break is 276 %.
Embodiment 2
(1) preparation of fire retardant zinc hydroxyl stannate-palygorskite clay
ZnCl with 10g
23H
2O is dissolved in the 100 ml zero(ppm) water, adds 60g palygorskite clay (attapulgite), is heated to 85 ℃, stirs 25 min.With HCl regulation system pH=5.0; Add 30 gSnCl
45H
2O, violent stirring 10 min, with final pH=9.0 of NaOH conditioned reaction system, crystallization 3 h under the room temperature, filtering precipitate, washing is put into baking oven then and is dried, and grinds the 300m sieve, obtains zinc hydroxyl stannate-palygorskite clay fire retardant.
(2) preparation of flame-proof polyvinyl chloride matrix material
With 10 g zinc hydroxyl stannate-palygorskite clay; 10 g wood powders; 4 g cupric oxide powders, 2 g stablizers (dibasicity O-phthalic lead plumbate), 10 g softening agent (Octyl adipate), 0.8 g lubricant (whiteruss) add in the 100 g SE matrixes; Through the method for melting mixing, prepared fire-retardant low cigarette polyvinyl chloride composite materials.
Each item performance of matrix material: oxygen index is 35, and horizontal firing reaches the HB-a level, and vertical combustion reaches the UL94V-0 level, and smoke density is 254 under the nonflame condition, and tensile strength is 11.9 MPa, and elongation at break is 263%.
Embodiment 3
(1) preparation of fire retardant zinc hydroxyl stannate-palygorskite clay
ZnCl with 10g
23H
2O is dissolved in the 100 ml zero(ppm) water, adds 80g palygorskite clay (attapulgite), is heated to 85 ℃, stirs 30 min.With HCl regulation system pH=5.0; Add 40 g SnCl
45H
2O, violent stirring 20 min, with final pH=9.0 of NaOH conditioned reaction system, crystallization 3 h under the room temperature, filtering precipitate, washing is put into baking oven then and is dried, and grinds the 300m sieve, obtains zinc hydroxyl stannate-palygorskite clay fire retardant.
(2) preparation of flame-proof polyvinyl chloride matrix material
With 15 g zinc hydroxyl stannate-palygorskite clay; 6 g wood powders; 5 g cupric oxide powders, 3 g stablizers (lead stearate), 20 g softening agent (Tritolyl Phosphate), 0.9 g lubricant (whiteruss) add in the 100 g SE matrixes; Through the method for melting mixing, prepared fire-retardant low cigarette polyvinyl chloride composite materials.
Each item performance of matrix material: oxygen index is 37, and horizontal firing reaches the HB-a level, and vertical combustion reaches the UL94V-0 level, and smoke density is 263 under the nonflame condition, and tensile strength is 12.3 MPa, and elongation at break is 248%.
Embodiment 4
(1) preparation of fire retardant zinc hydroxyl stannate-palygorskite clay
ZnCl with 10g
23H
2O is dissolved in the 100 ml zero(ppm) water, adds 100 g palygorskite clay (attapulgite), is heated to 90 ℃, stirs 30 min.With HCl regulation system pH=6.0; Add 50 gSnCl
45H
2O, violent stirring 15 min, with final pH=9.4 of NaOH conditioned reaction system, crystallization 4 h under the room temperature, filtering precipitate, washing is put into baking oven then and is dried, and grinds the 300m sieve, obtains zinc hydroxyl stannate-palygorskite clay fire retardant.
(2) preparation of flame-proof polyvinyl chloride matrix material
With 20 g zinc hydroxyl stannate-palygorskite clay; 9 g wood powders; 6 g cupric oxide powders, 4 g stablizers (dibasic lead stearate), 25 g softening agent (phosphate toluene diphenyl ester), 1.0 g lubricants (Triple Pressed Stearic Acid) add in the 100 g SE matrixes; Through the method for melting mixing, prepared fire-retardant low cigarette polyvinyl chloride composite materials.
Each item performance of matrix material: oxygen index is 36, and horizontal firing reaches the HB-a level, and vertical combustion reaches the UL94V-0 level, and smoke density is 280 under the nonflame condition, and tensile strength is 12.7 MPa, and elongation at break is 240 %.
Embodiment 5
(1) preparation of fire retardant zinc hydroxyl stannate-palygorskite clay
ZnCl with 10g
23H
2O is dissolved in the 100 ml zero(ppm) water, adds 150g palygorskite clay (attapulgite), is heated to 90 ℃, stirs 35 min.With HCl regulation system pH=6.0; Add 35 gSnCl
45H
2O, violent stirring 15 min, with final pH=9.4 of NaOH conditioned reaction system, crystallization 4 h under the room temperature, filtering precipitate, washing is put into baking oven then and is dried, and grinds the 300m sieve, obtains zinc hydroxyl stannate-palygorskite clay fire retardant.
(2) preparation of flame-proof polyvinyl chloride matrix material
With 25 g zinc hydroxyl stannate-palygorskite clay; 12 g wood powders; 7 g cupric oxide powders, 4.5 g stablizers (silica gel co-precipitation lead silicate), 30 g softening agent (epoxidised soybean oil), 1.2 g lubricants (Triple Pressed Stearic Acid) add in the 100 g SE matrixes; Through the method for melting mixing, prepared fire-retardant low cigarette polyvinyl chloride composite materials.
Each item performance of matrix material: oxygen index is 34.7, and horizontal firing reaches the HB-a level, and vertical combustion reaches the UL94V-0 level, and smoke density is 241 under the nonflame condition, and tensile strength is 13.0 MPa, and elongation at break is 231 %.
Embodiment 6
(1) preparation of fire retardant zinc hydroxyl stannate-palygorskite clay
ZnCl with 10g
23H
2O is dissolved in the 100 ml zero(ppm) water, adds 200 g palygorskite clay (attapulgite), is heated to 95 ℃, stirs 40 min.With HCl regulation system pH=6.4; Add 45 gSnCl
45H
2O, violent stirring 25 min, with final pH=9.2 of NaOH conditioned reaction system, crystallization 5 h under the room temperature, filtering precipitate, washing is put into baking oven then and is dried, and grinds, crosses the 300m sieve, obtains zinc hydroxyl stannate-palygorskite clay fire retardant.
(2) preparation of flame-proof polyvinyl chloride matrix material
With 45 g zinc hydroxyl stannate-palygorskite clay; 15 g wood powders; 10 g cupric oxide powders, 5 g stablizers (white lead), 40 g softening agent (hexanodioic acid Ucar 35), 1.5 g lubricants (Triple Pressed Stearic Acid) add in the 100 g SE matrixes; Through the method for melting mixing, prepared fire-retardant low cigarette polyvinyl chloride composite materials.
Each item performance ability of matrix material: oxygen index is 35.5, and horizontal firing reaches the HB-a level, and vertical combustion reaches the UL94V-0 level, and smoke density is 285 under the nonflame condition, and tensile strength is 113.6 MPa, and elongation at break is 210 %.
Claims (9)
1. zinc hydroxyl stannate-palygorskite clay mixture is to be prepared from following process step: with ZnCl
23H
2O is soluble in water, adds ZnCl
23H
2The palygorskite clay that the O quality is 5 ~ 20 times is heated to 80 ~ 95 ℃, stirs 20 ~ 40min; The pH of regulation system=5.0 ~ 6.4; Add ZnCl
23H
2The SnCl that the O quality is 2 ~ 5 times
45H
2O stirs 10 ~ 25min; The final pH of conditioned reaction system=9.0 ~ 9.4, room temperature crystallization 3 ~ 5 h, filtering precipitate, washing, oven dry is ground, and obtains zinc hydroxyl stannate-palygorskite clay mixture.
According to claim 1 zinc hydroxyl stannate-palygorskite clay mixture as fire retardant in the application of preparation in the flame retarded polymeric material.
Like the said zinc hydroxyl stannate of claim 2-palygorskite clay mixture as fire retardant in the application of preparation in the flame retarded polymeric material, it is characterized in that: be used to prepare the flame-proof polyvinyl chloride matrix material.
Like the said zinc hydroxyl stannate of claim 3-palygorskite clay mixture as fire retardant in the application of preparation in the flame retarded polymeric material; It is characterized in that: with zinc hydroxyl stannate-palygorskite clay mixture is fire retardant; With the SE is matrix, and the method through melting mixing makes; The addition of said fire retardant zinc hydroxyl stannate-palygorskite clay is 5 ~ 45% of a SE substrate quality.
Like the said zinc hydroxyl stannate of claim 3-palygorskite clay mixture as fire retardant in the application of preparation in the flame retarded polymeric material, it is characterized in that: 5 ~ 15% the wood powder that adds the SE substrate quality.
Like the said zinc hydroxyl stannate of claim 3-palygorskite clay mixture as fire retardant in the application of preparation in the flame retarded polymeric material, it is characterized in that: 3 ~ 10% the cupric oxide powder that adds the SE substrate quality.
Like the said zinc hydroxyl stannate of claim 3-palygorskite clay mixture as fire retardant in the application of preparation in the flame retarded polymeric material, it is characterized in that: 1 ~ 5% the stablizer that adds the SE substrate quality.
Like the said zinc hydroxyl stannate of claim 3-palygorskite clay mixture as fire retardant in the application of preparation in the flame retarded polymeric material, it is characterized in that: 5 ~ 40% the softening agent that adds the SE substrate quality.
Like the said zinc hydroxyl stannate of claim 3-palygorskite clay mixture as fire retardant in the application of preparation in the flame retarded polymeric material, it is characterized in that: 0.5 ~ 1.5% the lubricant that adds the SE substrate quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110404724.9A CN102515185B (en) | 2011-12-08 | 2011-12-08 | Zinc hydroxystannate-palygorskite clay compound, its preparation and application as fire retardant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110404724.9A CN102515185B (en) | 2011-12-08 | 2011-12-08 | Zinc hydroxystannate-palygorskite clay compound, its preparation and application as fire retardant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102515185A true CN102515185A (en) | 2012-06-27 |
| CN102515185B CN102515185B (en) | 2014-02-05 |
Family
ID=46286337
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110404724.9A Active CN102515185B (en) | 2011-12-08 | 2011-12-08 | Zinc hydroxystannate-palygorskite clay compound, its preparation and application as fire retardant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102515185B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254531A (en) * | 2013-05-27 | 2013-08-21 | 常州大学 | Flame-retardant PVC (polyvinyl chloride) composite material and preparation method thereof |
| CN104086920A (en) * | 2014-07-18 | 2014-10-08 | 东北林业大学 | Flame-retardant smoke-suppression type PVC-based wood-plastic composite material and preparation method thereof |
| CN104119614A (en) * | 2014-08-12 | 2014-10-29 | 西北师范大学 | Preparation and application of zinc hydroxystannate-palygorskite-trithiocyanuric acid compound smoke-suppressed fire retardant |
| CN104140557A (en) * | 2014-08-12 | 2014-11-12 | 西北师范大学 | Preparation and application of zinc hydroxystannate-palygorskite-mercaptan composite flame retardant |
| CN104893248A (en) * | 2015-05-27 | 2015-09-09 | 河北大学 | Preparation method and application of inorganic hybrid smoke-suppression flame retardant |
| CN105949587A (en) * | 2016-07-18 | 2016-09-21 | 西北师范大学 | Preparing method of composite smoke suppression agent and application to preparing low-smoke cross-linking low density polyethylene |
| CN109181164A (en) * | 2018-09-07 | 2019-01-11 | 徐州赛欧电子科技有限公司 | A kind of preparation method of low-smoke and flame retardant rubber cable material |
| CN109517220A (en) * | 2018-11-13 | 2019-03-26 | 云南锡业集团（控股）有限责任公司研发中心 | A kind of preparation method of nanometer of tinbase expanding fire retardant |
| CN111041816A (en) * | 2019-12-09 | 2020-04-21 | 南通吉美装饰材料有限公司 | Preparation of flame-retardant smoke-suppressing PVC film |
| CN112143036A (en) * | 2020-08-25 | 2020-12-29 | 蚌埠壹石通聚合物复合材料有限公司 | Preparation method of nano zinc hydroxystannate/clay composite smoke suppressant |
| JPWO2021111504A1 (en) * | 2019-12-02 | 2021-06-10 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990009962A1 (en) * | 1989-02-22 | 1990-09-07 | Barry, Beresford, Thomas, Kingcome | Stannates and hydroxystannates |
| CN1304880A (en) * | 2000-07-19 | 2001-07-25 | 云南锡业公司 | Process for preparing powdered zinc hydroxytannate |
| JP2005272257A (en) * | 2004-03-26 | 2005-10-06 | Tateho Chem Ind Co Ltd | Complex metal hydroxide solid solution and its production method, resin composition containing the same and semiconductor device |
| CN1907862A (en) * | 2005-08-04 | 2007-02-07 | 河南大学 | Method of preparing nano hydroxyl zinc stannate and nano zinc stannate |
-
2011
- 2011-12-08 CN CN201110404724.9A patent/CN102515185B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990009962A1 (en) * | 1989-02-22 | 1990-09-07 | Barry, Beresford, Thomas, Kingcome | Stannates and hydroxystannates |
| CN1304880A (en) * | 2000-07-19 | 2001-07-25 | 云南锡业公司 | Process for preparing powdered zinc hydroxytannate |
| JP2005272257A (en) * | 2004-03-26 | 2005-10-06 | Tateho Chem Ind Co Ltd | Complex metal hydroxide solid solution and its production method, resin composition containing the same and semiconductor device |
| CN1907862A (en) * | 2005-08-04 | 2007-02-07 | 河南大学 | Method of preparing nano hydroxyl zinc stannate and nano zinc stannate |
Non-Patent Citations (1)
| Title |
|---|
| 刘建州,谢吉星,印杰,屈红强,徐建中: "羟基锡酸锌包覆纳米氢氧化镁在PVC中的应用", 《塑料科技》 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254531A (en) * | 2013-05-27 | 2013-08-21 | 常州大学 | Flame-retardant PVC (polyvinyl chloride) composite material and preparation method thereof |
| CN104086920A (en) * | 2014-07-18 | 2014-10-08 | 东北林业大学 | Flame-retardant smoke-suppression type PVC-based wood-plastic composite material and preparation method thereof |
| CN104140557B (en) * | 2014-08-12 | 2017-01-11 | 西北师范大学 | Preparation and application of zinc hydroxystannate-palygorskite-mercaptan composite flame retardant |
| CN104140557A (en) * | 2014-08-12 | 2014-11-12 | 西北师范大学 | Preparation and application of zinc hydroxystannate-palygorskite-mercaptan composite flame retardant |
| CN104119614A (en) * | 2014-08-12 | 2014-10-29 | 西北师范大学 | Preparation and application of zinc hydroxystannate-palygorskite-trithiocyanuric acid compound smoke-suppressed fire retardant |
| CN104893248A (en) * | 2015-05-27 | 2015-09-09 | 河北大学 | Preparation method and application of inorganic hybrid smoke-suppression flame retardant |
| CN104893248B (en) * | 2015-05-27 | 2017-01-11 | 河北大学 | Preparation method and application of inorganic hybrid smoke-suppression flame retardant |
| CN105949587A (en) * | 2016-07-18 | 2016-09-21 | 西北师范大学 | Preparing method of composite smoke suppression agent and application to preparing low-smoke cross-linking low density polyethylene |
| CN109181164A (en) * | 2018-09-07 | 2019-01-11 | 徐州赛欧电子科技有限公司 | A kind of preparation method of low-smoke and flame retardant rubber cable material |
| CN109517220A (en) * | 2018-11-13 | 2019-03-26 | 云南锡业集团（控股）有限责任公司研发中心 | A kind of preparation method of nanometer of tinbase expanding fire retardant |
| JPWO2021111504A1 (en) * | 2019-12-02 | 2021-06-10 | ||
| WO2021111504A1 (en) * | 2019-12-02 | 2021-06-10 | タキロンシーアイ株式会社 | Sheet for blasting method |
| JP7336538B2 (en) | 2019-12-02 | 2023-08-31 | タキロンシーアイ株式会社 | Sheet for blasting method |
| CN111041816A (en) * | 2019-12-09 | 2020-04-21 | 南通吉美装饰材料有限公司 | Preparation of flame-retardant smoke-suppressing PVC film |
| CN112143036A (en) * | 2020-08-25 | 2020-12-29 | 蚌埠壹石通聚合物复合材料有限公司 | Preparation method of nano zinc hydroxystannate/clay composite smoke suppressant |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102515185B (en) | 2014-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102515185B (en) | Zinc hydroxystannate-palygorskite clay compound, its preparation and application as fire retardant | |
| CN110218401B (en) | Flame-retardant smoke-inhibiting soft polyvinyl chloride composite material with good mechanical property and preparation method thereof | |
| CN101280142B (en) | Preparation method of environment-friendly aqueous nanometer fireproof flame-retardant coating | |
| CN102453290B (en) | Flame-retarding smoke-inhibiting PVC wood plastic composite foamed material and manufacturing method thereof | |
| CN102120856B (en) | Polyvinyl chloride/organic hydrotalcite nanocomposite and preparation method thereof | |
| CN104744791B (en) | A kind of low smoke halogen-free fire retardant polyolefin cable material and preparation method thereof | |
| CN102276934A (en) | Environmental-friendly CPE rubber sheathing material with low temperature resistance and oil-resistance and flame retardancy, and preparation method thereof | |
| CN102807695A (en) | Low smoke halogen-free flame retardant sheath material for optical fiber cable, and preparation method thereof | |
| CN104140598A (en) | Halogen-free flame-retardance anti-static polypropylene composite material and preparation methods thereof | |
| CN1787120A (en) | Thermoplastic non-halogen low fume fire resistant cable isolation material and processing tech. thereof | |
| CN102254594A (en) | Double-layer metal cladded flame-retardant electric cable | |
| CN104119614B (en) | The Synthesis and applications of zinc hydroxyl stannate-polygorskite-trithiocyanuric acid compound smoke inhibition fire retardant | |
| CN105566811A (en) | Composite halogen-free flame-retardant smoke suppression agent of PVC wood-plastic composite material and preparation method and application of agent | |
| CN102352057B (en) | Non-halogen composite flame retardant and application thereof in preparation of flame retardant thermoplastic elastomer composite | |
| CN103788530A (en) | Low-smoke low-halogen flame-retardant insulation-grade PVC (polyvinyl chloride) sheath material for ultrahigh-voltage cable, and preparation of low-smoke low-halogen flame-retardant insulation-grade PVC sheath material | |
| CN102531459B (en) | Fireproof seal daub and preparation method thereof | |
| CN105670154A (en) | PVC flame-retardant fire-protection threading pipe | |
| CN109608732A (en) | A kind of anti-electrostatic fire retardant type polyethylene composition, particle, tubing and its preparation method and the purposes as coal mine tubing | |
| CN108219319A (en) | A kind of flame resistant cable material | |
| CN104592673A (en) | Polyvinyl chloride Grade-A flame-retardant fireproof silencing wear-resistant wood-plastic floor material | |
| CN105001561A (en) | Flame retardant polyvinyl chloride composition and preparation method thereof | |
| CN102558714A (en) | Polyvinyl chloride/modified nano montmorillonite compound material and preparation method thereof | |
| CN104448490A (en) | Halogen-free intumescent flame-retardant polyethylene cable material and preparation method thereof | |
| CN104592675A (en) | Polyvinyl chloride Grade-A flame-retardant fireproof wear-resistant wood-plastic floor material | |
| CN104140557B (en) | Preparation and application of zinc hydroxystannate-palygorskite-mercaptan composite flame retardant |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201209 Address after: No.33 Hengyang South Road, Jinhu County, Huaian City, Jiangsu Province 211600 Patentee after: Jinhu agricultural and sideline products Marketing Association Address before: 730070 No. 967 Anning East Road, Anning District, Gansu, Lanzhou Patentee before: Northwest Normal University |
|
| TR01 | Transfer of patent right |