CN101914217A - Environmentally-friendly flame retardant for substituting antimony trioxide - Google Patents
Environmentally-friendly flame retardant for substituting antimony trioxide Download PDFInfo
- Publication number
- CN101914217A CN101914217A CN 201010239899 CN201010239899A CN101914217A CN 101914217 A CN101914217 A CN 101914217A CN 201010239899 CN201010239899 CN 201010239899 CN 201010239899 A CN201010239899 A CN 201010239899A CN 101914217 A CN101914217 A CN 101914217A
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- CN
- China
- Prior art keywords
- flame retardant
- antimonous oxide
- raw material
- antimony trioxide
- environmental protection
- 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
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- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical group O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000003063 flame retardant Substances 0.000 title abstract description 46
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 28
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000007613 environmental effect Effects 0.000 claims abstract description 15
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004327 boric acid Substances 0.000 claims abstract description 10
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000391 magnesium silicate Substances 0.000 claims abstract description 10
- 229910052919 magnesium silicate Inorganic materials 0.000 claims abstract description 10
- 235000019792 magnesium silicate Nutrition 0.000 claims abstract description 10
- 239000011787 zinc oxide Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003340 retarding agent Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical group [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000012856 packing Methods 0.000 claims description 7
- 238000010298 pulverizing process Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 239000003125 aqueous solvent Substances 0.000 claims description 2
- 239000004033 plastic Substances 0.000 abstract description 4
- 229920003023 plastic Polymers 0.000 abstract description 4
- 229920001971 elastomer Polymers 0.000 abstract description 3
- 229920006351 engineering plastic Polymers 0.000 abstract description 3
- 229920000098 polyolefin Polymers 0.000 abstract description 3
- 230000008030 elimination Effects 0.000 abstract description 2
- 238000003379 elimination reaction Methods 0.000 abstract description 2
- 239000000779 smoke Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 229910052787 antimony Inorganic materials 0.000 description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 229920007019 PC/ABS Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 102220040412 rs587778307 Human genes 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Abstract
The invention discloses an environmentally-friendly flame retardant for substituting antimony trioxide. The flame retardant is prepared from the following raw materials in part by weight: 45 to 60 parts of antimony trioxide, 8 to 12 parts of zinc oxide, 38 to 45 parts of boric acid, 3 to 5 parts of magnesium silicate and 0.8 to 1.2 parts of catalyst. The flame retardant has the functions of flame resistance and smoke elimination, and can substitute the antimony trioxide; the flame resistance of the flame retardant is better than that of the antimony trioxide, and the price of the flame retardant is about 20 percent lower than that of the antimony trioxide; the consumption of the flame retardant is the same as or even less than that of the antimony trioxide in application; and on the aspect of environmental protection, the index of the flame retardant is superior to that of the antimony trioxide. The flame retardant can equivalently substitute the antimony trioxide in PVC, polyolefin plastic, engineering plastic, rubber and unsaturated resin.
Description
Technical field
The present invention relates to a kind of fire retardant, specifically is a kind of environmental protection fire retarding agent that can substitute antimonous oxide (stibium trioxide).
Background technology
Antimonous oxide is commonly called as stibium trioxide, is a kind of intermediate oxide, and pulverability is little, and is heat-resisting, and heating flavescence look returns white after the cooling.Antimonous oxide cooperates with halogen contained compound, plays fire retardation in their thermal decomposition process, and fire retardant rate height is little for the influence of base material mechanical property, is widely used in using as fire retardant in the plastics such as PVC, PP, PE, ABS, PU.But at present the exploitation of antimony ore but is restricted, and Ministry of Land and Resources has issued " notice of tungsten ore antimony ore in 2009 and rare-earth mineral exploitation overall control index " in April, 2009, represent that national antimony ore in 2009 exploits 90180 tons of overall control indexs.Ministry of Land and Resources's in March, 2010 decision continues antimony ore is carried out exploitation overall control management; National antimony ore (amount of metal) exploitation overall control index was 100000 tons in 2010; Before 30 days June in 2011, time-out is accepted new antimony ore and is reconnoitred, exploits application for registration in principle.
Along with in limit resource exploitation list policy enforcement is listed antimony by country, the price of antimonous oxide is surging day by day.In order to reduce cost, press for the novel environment friendly fire retardant that release can substitute antimonous oxide.
Summary of the invention
The object of the present invention is to provide a kind of environmental protection fire retarding agent that can substitute antimonous oxide, this fire retardant fully can the equivalent substitution antimonous oxide in PVC, polyolefin plastics, engineering plastics, rubber and unsaturated polyester.Flame retardant properties is than antimonous oxide better effects if, and price is lower by 20% than antimonous oxide, and environmental protection index is better than antimonous oxide.
Technical scheme of the present invention is: a kind of environmental protection fire retarding agent of alternative antimonous oxide, it is characterized in that, and make antimonous oxide 45-60, zinc oxide 8-12, boric acid 38-45, Magnesium Silicate q-agent 3-5, catalyzer 0.8-1.2 by the raw material of following weight parts.Described catalyzer is preferably zinc borate.
Preparation method: take by weighing raw material for standby by above-mentioned weight part, add raw material total mass 5-8 water doubly in the reactor earlier, then raw material is added stirring and dissolving in the reactor as solvent; It is 100-110 ℃ that reactor is steam heated to temperature, and reaction is 12 hours under this temperature, through washing (removing most water), centrifugal drying, pulverizing, packing, obtains product of the present invention then.Described temperature of reaction is preferably 104-106 ℃; The amount of described aqueous solvent is preferably 6 times of raw material total mass.
The preferred technical solution of the present invention is: a kind of environmental protection fire retarding agent of alternative antimonous oxide, it is characterized in that, and make antimonous oxide 50, zinc oxide 10, boric acid 42, Magnesium Silicate q-agent 4, zinc borate 1 by the raw material of following weight parts.
The invention has the beneficial effects as follows: product of the present invention has fire-retardant, smoke elimination function, can substitute antimonous oxide; And its flame retardant properties is than antimonous oxide better effects if, and price is lower by about 20% than antimonous oxide; Identical with the antimonous oxide consumption even still less on using; The environmental protection aspect, index is better than antimonous oxide.But this fire retardant is the equivalent substitution antimonous oxide in PVC, polyolefin plastics, engineering plastics, rubber and unsaturated polyester.Performance index of the present invention are as shown in table 1 below.
The performance index of table 1 product of the present invention
Embodiment
Embodiment 1
Proportioning: antimonous oxide 50, zinc oxide 10, boric acid 42, Magnesium Silicate q-agent 4, zinc borate 1.
The preparation method: take by weighing raw material for standby by above-mentioned weight part, the water that adds 6 times of raw material total masses earlier in the reactor adds raw material stirring and dissolving in the reactor then as solvent; It is 104-106 ℃ that reactor is steam heated to temperature, and reaction is 12 hours under this temperature, through washing (removing most water), centrifugal drying, pulverizing, packing, obtains product of the present invention then.
The environmental protection fire retarding agent of the alternative antimonous oxide of products obtained therefrom (hereafter stibium trioxide equivalence fire retardant) is as follows with the effect of antimonous oxide:
1, the application of stibium trioxide equivalence fire retardant in PP
In PP (T30S), TDE with 21% is a main flame retardant, respectively with 7% antimonous oxide and stibium trioxide equivalence fire retardant as synergistic flame retardant, after adding a certain amount of talcum powder, after using prepared in twin-screw extruder to become modifying material, after injecting standard sample of photo with injection moulding machine, test its performance.Result such as table 2:
Table 2 PP test result
Experimental data shows that stibium trioxide equivalence fire retardant can substitute antimonous oxide in PP, little to every performance impact of PP.
2, the application of stibium trioxide equivalence fire retardant in PA6
In 30% glass enhanced PA6, TDE with 12% is a main flame retardant, respectively with 4% antimonous oxide and stibium trioxide equivalence fire retardant as synergistic flame retardant, use prepared in twin-screw extruder to become modifying material after, after injecting standard sample of photo with injection moulding machine, test its performance.Result such as table 3:
Table 3 PA6 test result
Experimental data shows that except that big to the bending property influence, all the other index influences are less, and stibium trioxide equivalence fire retardant can replace antimonous oxide in PA6.
3, the application of stibium trioxide equivalence fire retardant in PBT
In 30% glass enhanced PBT, TDE with 9% is a main flame retardant, respectively with 3% antimonous oxide and stibium trioxide equivalence fire retardant as synergistic flame retardant, use prepared in twin-screw extruder to become modifying material after, after injecting standard sample of photo with injection moulding machine, test its performance.Result such as table 4:
Table 4 PBT test result
Test data shows that stibium trioxide equivalence fire retardant can replace antimonous oxide in the PBT flame-retardant formulations, and every index influence is less.
4, the application of stibium trioxide equivalence fire retardant in ABS
In ABS, the tetrabromo-bisphenol with 20% is a main flame retardant, respectively with 5% antimonous oxide and stibium trioxide equivalence fire retardant as synergistic flame retardant, use prepared in twin-screw extruder to become modifying material after, inject standard sample of photo with injection moulding machine after, test its performance.Result such as table 5:
Table 5 ABS test result
Experimental data shows that except that the impact performance impact was big, all the other index influences were less, and stibium trioxide equivalence fire retardant can replace antimonous oxide in ABS.
5, the application of stibium trioxide equivalence fire retardant in PC/ABS
In PC/ABS (7: 3), tetrabromo-bisphenol with 5% is a main flame retardant, respectively with 2% antimonous oxide and stibium trioxide equivalence fire retardant as synergistic flame retardant, use prepared in twin-screw extruder to become modifying material after, after injecting standard sample of photo with injection moulding machine, test its performance.Result such as table 6:
Table 6 PC/ABS test result
Test data shows that notch shock is decreased, and molten finger increases to some extent, and flexural strength has a more substantial increase, and stibium trioxide equivalence fire retardant can replace antimonous oxide in the PC/ABS flame-retardant formulations.
Embodiment 2
Proportioning: antimonous oxide 55, zinc oxide 11, boric acid 40, Magnesium Silicate q-agent 5, zinc borate 1.2.
The preparation method: take by weighing raw material for standby by above-mentioned weight part, the water that adds 5 times of raw material total masses earlier in the reactor adds raw material stirring and dissolving in the reactor then as solvent; It is 100-105 ℃ that reactor is steam heated to temperature, and reaction is 12 hours under this temperature, through washing (removing most water), centrifugal drying, pulverizing, packing, obtains product of the present invention then.
Embodiment 3
Proportioning: antimonous oxide 60, zinc oxide 12, boric acid 45, Magnesium Silicate q-agent 5, zinc borate 1.
The preparation method: take by weighing raw material for standby by above-mentioned weight part, the water that adds 6.5 times of raw material total masses earlier in the reactor adds raw material stirring and dissolving in the reactor then as solvent; It is 105-110 ℃ that reactor is steam heated to temperature, and reaction is 12 hours under this temperature, through washing (removing most water), centrifugal drying, pulverizing, packing, obtains product of the present invention then.
Embodiment 4
Proportioning: antimonous oxide 45, zinc oxide 8, boric acid 39, Magnesium Silicate q-agent 3.5, zinc borate 0.8.
The preparation method: take by weighing raw material for standby by above-mentioned weight part, the water that adds 7 times of raw material total masses earlier in the reactor adds raw material stirring and dissolving in the reactor then as solvent; It is 104-108 ℃ that reactor is steam heated to temperature, and reaction is 12 hours under this temperature, through washing (removing most water), centrifugal drying, pulverizing, packing, obtains product of the present invention then.
Embodiment 5
Proportioning: antimonous oxide 48, zinc oxide 9, boric acid 38, Magnesium Silicate q-agent 3, zinc borate 0.8.
The preparation method: take by weighing raw material for standby by above-mentioned weight part, the water that adds 6 times of raw material total masses earlier in the reactor adds raw material stirring and dissolving in the reactor then as solvent; It is 102-106 ℃ that reactor is steam heated to temperature, and reaction is 12 hours under this temperature, through washing (removing most water), centrifugal drying, pulverizing, packing, obtains product of the present invention then.
Claims (6)
1. the environmental protection fire retarding agent of an alternative antimonous oxide is characterized in that, is made antimonous oxide 45-60, zinc oxide 8-12, boric acid 38-45, Magnesium Silicate q-agent 3-5, catalyzer 0.8-1.2 by the raw material of following weight parts.
2. the environmental protection fire retarding agent of a kind of alternative antimonous oxide as claimed in claim 1 is characterized in that, described catalyzer is a zinc borate.
3. the environmental protection fire retarding agent of a kind of alternative antimonous oxide as claimed in claim 2 is characterized in that, is made antimonous oxide 50, zinc oxide 10, boric acid 42, Magnesium Silicate q-agent 4, zinc borate 1 by the raw material of following weight parts.
4. the environmental protection fire retarding agent preparation method of claim 1 or 3 described alternative antimonous oxides, it is characterized in that, take by weighing raw material for standby by claim 1 or 3 described weight parts, add raw material total mass 5-8 water doubly in the reactor earlier, then raw material is added stirring and dissolving in the reactor as solvent; It is 100-110 ℃ that reactor is steam heated to temperature, and reaction is 12 hours under this temperature, through washing, centrifugal drying, pulverizing, packing, obtains product then.
5. the environmental protection fire retarding agent preparation method of alternative antimonous oxide as claimed in claim 4 is characterized in that, described temperature of reaction is 104-106 ℃.
6. the environmental protection fire retarding agent preparation method of alternative antimonous oxide as claimed in claim 4 is characterized in that, the amount of described aqueous solvent is 6 times of raw material total mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102398994A CN101914217B (en) | 2010-07-29 | 2010-07-29 | Environmentally-friendly flame retardant for substituting antimony trioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102398994A CN101914217B (en) | 2010-07-29 | 2010-07-29 | Environmentally-friendly flame retardant for substituting antimony trioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101914217A true CN101914217A (en) | 2010-12-15 |
| CN101914217B CN101914217B (en) | 2011-12-28 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2010102398994A Active CN101914217B (en) | 2010-07-29 | 2010-07-29 | Environmentally-friendly flame retardant for substituting antimony trioxide |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103849005A (en) * | 2012-12-04 | 2014-06-11 | 深圳市联合鑫科技有限公司 | Efficient and environment-friendly flame retardant |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1261904A (en) * | 1997-06-30 | 2000-08-02 | 西巴特殊化学品控股有限公司 | Flame retardant compositions |
| CN100999669A (en) * | 2006-12-29 | 2007-07-18 | 江苏工业学院 | Preparation process of nano concave soil base inorganic flame-retarded agent |
-
2010
- 2010-07-29 CN CN2010102398994A patent/CN101914217B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1261904A (en) * | 1997-06-30 | 2000-08-02 | 西巴特殊化学品控股有限公司 | Flame retardant compositions |
| CN100999669A (en) * | 2006-12-29 | 2007-07-18 | 江苏工业学院 | Preparation process of nano concave soil base inorganic flame-retarded agent |
Non-Patent Citations (1)
| Title |
|---|
| 《无机盐工业》 20071231 张月琴等 硼酸锌的性质、制备及阻燃应用 第9-12页 1-6 第39卷, 第12期 2 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103849005A (en) * | 2012-12-04 | 2014-06-11 | 深圳市联合鑫科技有限公司 | Efficient and environment-friendly flame retardant |
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| Publication number | Publication date |
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| CN101914217B (en) | 2011-12-28 |
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Address after: 250204 Luxi Luye Road, Diaozhen Chemical Park, Mingshui Economic and Technological Development Zone, Zhangqiu District, Jinan City, Shandong Province Patentee after: Shandong Taixing New Materials Co.,Ltd. Address before: 250101 Building 3, North District, University Science Park, Jinan High-tech Zone, Shandong Province Patentee before: JINAN TAIXING FINE CHEMICALS CO.,LTD. |
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Denomination of invention: An environmentally friendly flame retardant instead of antimony trioxide Effective date of registration: 20201119 Granted publication date: 20111228 Pledgee: Bank of Beijing Co.,Ltd. Jinan Branch Pledgor: Shandong Taixing New Materials Co.,Ltd. Registration number: Y2020980008268 |
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Date of cancellation: 20221114 Granted publication date: 20111228 Pledgee: Bank of Beijing Co.,Ltd. Jinan Branch Pledgor: Shandong Taixing New Materials Co.,Ltd. Registration number: Y2020980008268 |
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Denomination of invention: An environment-friendly flame retardant instead of antimony trioxide Effective date of registration: 20221224 Granted publication date: 20111228 Pledgee: Bank of Beijing Co.,Ltd. Jinan Branch Pledgor: Shandong Taixing New Materials Co.,Ltd. Registration number: Y2022980027519 |