CN105670259B - A kind of polyborosiloxane fire retardant and the polycarbonate composite material and preparation method thereof containing polyborosiloxane fire retardant - Google Patents
A kind of polyborosiloxane fire retardant and the polycarbonate composite material and preparation method thereof containing polyborosiloxane fire retardant Download PDFInfo
- Publication number
- CN105670259B CN105670259B CN201410673776.XA CN201410673776A CN105670259B CN 105670259 B CN105670259 B CN 105670259B CN 201410673776 A CN201410673776 A CN 201410673776A CN 105670259 B CN105670259 B CN 105670259B
- Authority
- CN
- China
- Prior art keywords
- fire retardant
- polyborosiloxane
- polycarbonate
- polyborosiloxane fire
- composite material
- 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.)
- Active
Links
Abstract
The present invention provides a kind of polyborosiloxane fire retardant, is the polyborosiloxane intermediate first by reacting generation after triethoxy borine, silicon tetrachloride, metallocene catalyst and co-catalyst；The hydrolysate that polyborosiloxane intermediate is reacted with silicon tetrachloride, distilled water is washed again, removes obtained, yield height, purity is high after small molecule；And polyborosiloxane fire retardant be transparence, high temperature resistant and be not easy to be precipitated；In addition polyborosiloxane molecular weight and molecualr weight distribution is controllable.A second object of the present invention is to provide a kind of polycarbonate composite materials and preparation method thereof containing polyborosiloxane fire retardant of high transparency halogen-free flameproof, polyborosiloxane fire retardant can significantly improve the flame retardant property and limit oxygen index of polycarbonate, and on the tensile property of composite material, bending property, impact property and the transparency without influence, especially its transparency and impact property.
Description
Technical field:
The present invention relates to polymer modification field more particularly to a kind of polyborosiloxane fire retardant and contain poly- borosilicate
The polycarbonate composite material and preparation method thereof of oxygen alkane fire retardant.
Background technique:
Polycarbonate (PC) is a kind of engineering plastics haveing excellent performance, and the transparency is good, and general light transmittance is 85% or more；
Flame retardant property reaches the flame retardant rating of UL94-V2, and its limit oxygen index LOI is about 26%.Now be widely applied to automobile,
The fields such as household electrical appliances, electronic apparatus.But the anti-flammability of PC is not able to satisfy the requirement of special occasions still, therefore is generally added in PC fire-retardant
To improve its anti-flammability, one of the most common fire retardant has bromide fire retardant, phosphate ester flame retardants, Sulfonates fire retardant for agent
Deng.But these fire retardant some will affect PC performance, and some meeting non-refractories are easily precipitated, and some will affect transparency etc..Such as:
Composite flame-retardant agent halogenated epoxy resin class, phosphoric acid ester, Polyhalogenated aromatic hydrocarbons, ten bromines are used in Chinese patent CN 1121451C
Diphenyl ether and their mixture, wherein phosphate ester flame retardants are easily precipitated, deca-BDE does not meet European Union RoHS environmental protection
It instructs and usage amount is larger, at 5 ~ 20 parts.In addition, China document " preparation and flame retardant property of polyborosiloxane " SILICONE
MATERIAL 2013,27(3): it is with diphenyl silanediol, hydroxy silicon oil, methyltriethoxysilane and boric acid in 162 ~ 164
Polyborosiloxane is prepared for raw material, this preparation method low yield, purity are low.
Summary of the invention:
The first purpose of this invention is to provide a kind of polyborosiloxane fire retardant that yield is high, with high purity, the second mesh
The polycarbonate composite material containing polyborosiloxane fire retardant for being to provide a kind of high transparency halogen-free flameproof and its preparation side
Method.
The technical scheme is that
A kind of polyborosiloxane fire retardant, the polyborosiloxane fire retardant is prepared by following methods:
(1) polyborosiloxane intermediate is prepared
Under nitrogen protection, by weight it is 100:(0.5 ~ 10 by triethoxy borine and silicon tetrachloride) reactor is added
In be placed in heating mantle and heated, stirred；Then 3 ~ 4 are reacted after being slowly added to metallocene catalyst and co-catalyst simultaneously
Hour, obtain polyborosiloxane intermediate；The additional amount of the metallocene catalyst account for triethoxy borine weight 0.005 ~
0.03%, the additional amount of co-catalyst accounts for the 0.01 ~ 0.05% of triethoxy borine weight；
(2) polyborosiloxane fire retardant is prepared
It is slowly added to account for 50 ~ 150% silicon tetrachloride and excessive distilled water of triethoxy borine weight into (1), after
Continuous reaction 3 ~ 4 hours hydrolysate, then to hydrolysate carry out after deionized water washing 110 ~ 120 DEG C at a temperature of into
Row vacuum distillation removal small molecule, finally obtains liquid polyborosiloxane fire retardant.
Further, metallocene catalyst is cyclopentadienyl titanium dichloride or bis cyclopentadienyl zirconium dichloride, co-catalyst three in the step (1)
Aluminium methyl or triethyl aluminum.
The time that metallocene catalyst and co-catalyst are slowly added in the step (1) is 30 ~ 40 minutes.
Temperature in the step (1) in reactor is 80 ~ 85 DEG C, mixing speed is 180 ~ 200 revs/min.
The addition time of silicon tetrachloride and distilled water is 10 ~ 15 minutes in the step (2).
The present invention has prepared polyborosiloxane fire retardant using metallocene catalysis system, and yield is high, with high purity；And it can
Control the molecular weight and molecualr weight distribution of polysiloxanes.
The second object of the present invention is to provide a kind of polycarbonate composite material containing above-mentioned polyborosiloxane fire retardant,
It is prepared by weight by following component:
100 parts of polycarbonate,
0.5 ~ 2 part of polyborosiloxane fire retardant,
0.2 ~ 0.5 part of dispersing agent,
0.2 ~ 0.5 part of antioxidant.
Further, the dispersing agent is organic silicon dispersing agent.
The antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester (anti-1076) and three
[2,4- di-tert-butyl-phenyl] phosphite ester (anti-168) compounding.
It is rapid as follows third object of the present invention is to provide the preparation method of above-mentioned polycarbonate composite material:
(1) by polycarbonate through 110 DEG C forced air drying 4 ~ 6 hours；
(2) by 100 parts of dry polycarbonate and 0.5 ~ 2 part of polyborosiloxane fire retardant in revolving speed be 200 ~ 300 revs/min
It is mixed 3 ~ 5 minutes in the high-speed mixer of clock；Be subsequently added into 0.2 ~ 0.5 part of dispersing agent, 0.2 ~ 0.5 part of antioxidant continues to mix 3 ~
5 minutes；
(3) material mixed is added twin-screw extrude into wire drawing and is granulated to obtain polycarbonate composite material；It is described double
The temperature of screw extruder is followed successively by 150 DEG C, 230 DEG C, 260 DEG C, 260 DEG C, 260 DEG C, 260 DEG C, 260 from feeding section to head
DEG C, 260 DEG C, 260 DEG C, 265 DEG C, screw diameter be 42 ~ 56 millimeters, screw slenderness ratio be 40 ~ 48.
The beneficial effects of the present invention are as follows:
1, the present invention catalyzes and synthesizes polyborosiloxane fire retardant using metallocene catalyst, and yield is high, with high purity；And poly- boron
Siloxane flame retardant be transparence, high temperature resistant and be not easy to be precipitated；In addition polyborosiloxane molecular weight and molecualr weight distribution is controllable, can
To prepare required molecular size range and molecular weight distribution as needed.
2, be added in polycarbonate using polyborosiloxane fire retardant of the invention as fire retardant can significantly improve it is poly-
The limit oxygen index of carbonic ester, and the tensile property to composite material, bending property, impact property and the transparency are without shadow
It rings, especially its transparency and impact property.
3, the additive amount of polyborosiloxane fire retardant is seldom, only accounts for the 0.5 ~ 2% of polycarbonate weight, at low cost, to multiple
The performance of condensation material influences small.
4, polycarbonate composite material prepared by the present invention is high transparency, and it is carried out in high volume for simple process, easily
Production.
Specific embodiment:
Below with reference to some embodiments, the invention will be further described with comparative example.Following embodiment is of the invention
Typical case, scope of protection of the present invention is not limited thereto.
Flame retardant property is tested according to UL-94 standard in following example；Limit oxygen index according to ASTM D2863 into
Row test；Light transmittance is tested according to ASTM D1003；Tensile property is tested according to ASTM D638, and (tensile speed is
20mm/min)；Bending property is tested (rate of bending 1.25mm/min) according to ASTM D790；Izod notched impact
Performance is tested according to ASTM D256.
The main raw material(s) used in embodiment and comparative example is as follows:
Polycarbonate model: PC-1100 producer: South Korea is carefree；
Triethoxy borine model: pure producer: Aladdin is analyzed；
Silicon tetrachloride model: pure producer: Aladdin is analyzed；
Cyclopentadienyl titanium dichloride model: without producer: Yueyang Kimoutain Sci-Tech Co., Ltd.；
Bis cyclopentadienyl zirconium dichloride model: without producer: Yueyang Kimoutain Sci-Tech Co., Ltd.；
Trimethyl aluminium model: without producer: Wuhan methyl Science and Technology Ltd.；
Triethyl aluminum model: without producer: Wuhan methyl Science and Technology Ltd.；
Dispersing agent model: E525 producer: German Degussa；
Antioxidant model: 1076 producers: Yixing City angel synthesizes chemistry；
Antioxidant model: 168 producers: Yixing City angel synthesizes chemistry.
Embodiment 1
(1) polyborosiloxane intermediate is prepared
Under nitrogen protection, 100 parts of triethoxy borines and 0.5 part of silicon tetrachloride are added in reactor and are placed in heating
It heated, stirred in set, heating temperature is 80 DEG C, mixing speed is 180 revs/min；Then it is slowly added to 0.005 simultaneously
Part metallocene catalyst cyclopentadienyl titanium dichloride and 0.01 part co-catalyst trimethyl aluminium 30 minutes, after then reacting 3 hours poly- boron
Silicone intermediate；
(2) polyborosiloxane fire retardant is prepared
50 parts of silicon tetrachlorides and excessive distilled water are slowly added into (1), it is 10 minutes that the time, which is added, is further continued for anti-
Answer 3 hours hydrolysate, then to hydrolysate carry out deionized water washing after 110 DEG C at a temperature of be evaporated under reduced pressure
Small molecule is removed, liquid polyborosiloxane fire retardant is finally obtained.
(3) polycarbonate composite material is prepared
By polycarbonate through 110 DEG C forced air drying 4 hours；
By 100 parts of dry polycarbonate and 0.5 part of liquid polyborosiloxane fire retardant in revolving speed be 200 revs/min
Room temperature is carried out in high-speed mixer to mix 3 minutes, be subsequently added into 0.2 part of dispersing agent E525,0.1 part of antioxidant 1076,0.1 part it is anti-
Oxygen agent 168 continuess to mix 3 minutes；
The material mixed is added twin-screw extrude into wire drawing granulation, transparent polycarbonate composite wood is made in cooling
Material.Wherein the temperature of double screw extruder be followed successively by from feeding section to head 150 DEG C, 230 DEG C, 260 DEG C, 260 DEG C, 260 DEG C,
260℃,260℃,260℃,260℃,265℃；Screw diameter is 42 millimeters, screw slenderness ratio 40.
The makrolon material of fire retardant of the present invention is not added in comparative example 1()
It will be through 110 DEG C of forced air drying 4 hours 100 parts of polycarbonates -1100,0.2 part of dispersing agent E525,0.1 part
Antioxidant 1076,0.1 part of irgasfos 168 room temperature in the high-speed mixer that revolving speed is 200 revs/min mix 3 minutes, then will mix
The material got togather add twin-screw extrude wire drawing be granulated, cooling polycarbonate composite material.Wherein double screw extruder
Temperature 150 DEG C, 230 DEG C, 260 DEG C, 260 DEG C, 260 DEG C, 260 DEG C, 260 DEG C, 260 DEG C, 260 are followed successively by from feeding section to head
℃,265℃.Screw diameter is 42 millimeters, screw slenderness ratio 40.
Embodiment 2
(1) polyborosiloxane intermediate is prepared
Under nitrogen protection, 100 parts of triethoxy borines and 10 parts of silicon tetrachlorides are added in reactor and are placed in heating
It heated, stirred in set, heating temperature is 85 DEG C, mixing speed is 200 revs/min；Then in same in 40 minutes
When be slowly added to 0.03 part of metallocene catalyst bis cyclopentadienyl zirconium dichloride and 0.05 part of co-catalyst triethyl aluminum, then react 4 hours
Polyborosiloxane intermediate is obtained afterwards；
(2) polyborosiloxane fire retardant is prepared
150 parts of silicon tetrachlorides and excessive distilled water are slowly added into (1), it is 15 minutes that the time, which is added, is further continued for
Reaction 4 hours hydrolysate, then to hydrolysate carry out deionized water washing after 120 DEG C at a temperature of carry out decompression steaming
It evaporates except small molecule, finally obtains liquid polyborosiloxane fire retardant.
(3) polycarbonate composite material is prepared
By polycarbonate through 110 DEG C forced air drying 6 hours；
The height for being 300 revs/min in revolving speed by 100 parts of dry polycarbonate and 2 parts of liquid polyborosiloxane fire retardants
Room temperature is carried out in fast mixing machine to mix 5 minutes, is subsequently added into 0.5 part of dispersing agent E525,0.3 part of antioxidant 1076,0.2 part of antioxygen
Agent 168 continuess to mix 5 minutes；
The material mixed is added twin-screw extrude into wire drawing granulation, transparent polycarbonate composite wood is made in cooling
Material.Wherein the temperature of double screw extruder be followed successively by from feeding section to head 150 DEG C, 230 DEG C, 260 DEG C, 260 DEG C, 260 DEG C,
260℃,260℃,260℃,260℃,265℃；Screw diameter is 56 millimeters, screw slenderness ratio 48.
Embodiment 3
(1) polyborosiloxane intermediate is prepared
Under nitrogen protection, 100 parts of triethoxy borines and 5 parts of silicon tetrachlorides are added in reactor and are placed in heating mantle
In heated, stirred, heating temperature is 83 DEG C, mixing speed is 190 revs/min；Then in 34 minutes simultaneously
It is slowly added to 0.015 part of metallocene catalyst cyclopentadienyl titanium dichloride and 0.029 part of co-catalyst triethyl aluminum, it is small then to react 3.2
When after polyborosiloxane intermediate；
(2) polyborosiloxane fire retardant is prepared
88 parts of silicon tetrachlorides and excessive distilled water are slowly added into (1), it is 15 minutes that the time, which is added, is further continued for anti-
Answer 3.4 hours hydrolysate, then to hydrolysate carry out deionized water washing after 115 DEG C at a temperature of carry out decompression steaming
It evaporates except small molecule, finally obtains liquid polyborosiloxane fire retardant.
(3) polycarbonate composite material is prepared
By polycarbonate through 110 DEG C forced air drying 4.8 hours；
By 100 parts of dry polycarbonate and 1.3 parts of liquid polyborosiloxane fire retardants in revolving speed be 245 revs/min
In high-speed mixer carry out room temperature mix 3.3 minutes, be subsequently added into 0.32 part dispersing agent E525,0.16 part of antioxidant 1076,
0.14 part of irgasfos 168 continuess to mix 3.6 minutes；
The material mixed is added twin-screw extrude into wire drawing granulation, transparent polycarbonate composite wood is made in cooling
Material.Wherein the temperature of double screw extruder be followed successively by from feeding section to head 150 DEG C, 230 DEG C, 260 DEG C, 260 DEG C, 260 DEG C,
260℃,260℃,260℃,260℃,265℃；Screw diameter is 48 millimeters, screw slenderness ratio 44.
Above-described embodiment 1-3 and the polycarbonate composite material of 1 preparation of comparison are examined according to coherent detection standard respectively
Survey respective flame retardant property, limit oxygen index, light transmittance, tensile strength, bending strength, bending modulus and Izod notched impact
Intensity, concrete outcome is as shown in following table -1:
- 1 embodiment 1 ~ 3 of table and 1 performance of comparative example
| Test item | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| UL-94 flame retardant property/1.6mm | V0 | 5VB | 5VB | V2 |
| Limit oxygen index/% | 35.6 | 46.3 | 41.7 | 24.3 |
| Light transmittance/% | 89 | 88 | 89 | 89 |
| Tensile strength/MPa | 62 | 61 | 62 | 63 |
| Bending strength/MPa | 91 | 90 | 92 | 92 |
| Bending modulus/MPa | 2380 | 2410 | 2420 | 2350 |
| Izod notched impact/(KJ/m2) | 82 | 78 | 83 | 84 |
It is evident that from above embodiments 1 ~ 3 and comparative example 1:
1, polyborosiloxane fire retardant prepared by the present invention is added in polycarbonate, has its composite material good
Flame retardant property, and it is remarkably improved the flame retardant property of polycarbonate composite material and the light transmission of limit oxygen index and polycarbonate
Rate, and on mechanical performances such as the tensile strength of polycarbonate, Izod notched impact strengths without influence；
2, comparative example 3 and comparative example 1 can be seen that, addition accounts for 1.3% polyborosiloxane fire retardant of polycarbonate weight
So that composite material reaches the 5VB grade of UL-94/1.6mm, limit oxygen index reaches 41.7%.So polycarbonate of the invention
Composite material not only has stronger anti-flammability, also has high transparency and high-mechanical property, can be applied to some specific necks
Domain.
The above disclosure is just a few specific examples of the present application, however, this application is not limited to this, any this field
Technical staff can think variation, should all fall in the protection domain of the application.
Claims (9)
1. a kind of preparation method of polyborosiloxane fire retardant, it is characterised in that: the polyborosiloxane fire retardant is by following
What method was prepared:
(1) polyborosiloxane intermediate is prepared
Under nitrogen protection, by weight it is 100:(0.5 ~ 10 by triethoxy borine and silicon tetrachloride) it is added in reactor simultaneously
It is placed in heating mantle and is heated, stirred；Then reaction 3 ~ 4 is small after being slowly added to metallocene catalyst and co-catalyst simultaneously
When, obtain polyborosiloxane intermediate；The additional amount of the metallocene catalyst account for triethoxy borine weight 0.005 ~
0.03%, the additional amount of co-catalyst accounts for the 0.01 ~ 0.05% of triethoxy borine weight；
(2) polyborosiloxane fire retardant is prepared
It is slowly added to account for 50 ~ 150% silicon tetrachloride and excessive distilled water of triethoxy borine weight into (1), continue anti-
Answer 3 ~ 4 hours hydrolysate, then to hydrolysate carry out deionized water washing after 110 ~ 120 DEG C at a temperature of subtract
Pressure distillation removal small molecule, finally obtains liquid polyborosiloxane fire retardant.
2. a kind of preparation method of polyborosiloxane fire retardant according to claim 1, it is characterised in that: the step
(1) metallocene catalyst is cyclopentadienyl titanium dichloride or bis cyclopentadienyl zirconium dichloride in, and co-catalyst is trimethyl aluminium or triethyl aluminum.
3. a kind of preparation method of polyborosiloxane fire retardant according to claim 1, it is characterised in that: the step
(1) time that metallocene catalyst and co-catalyst are slowly added in is 30 ~ 40 minutes.
4. a kind of preparation method of polyborosiloxane fire retardant according to claim 1, it is characterised in that: the step
(1) temperature in reactor is 80 ~ 85 DEG C, mixing speed is 180 ~ 200 revs/min.
5. a kind of preparation method of polyborosiloxane fire retardant according to claim 1, it is characterised in that: the step
(2) the addition time of silicon tetrachloride and distilled water is 10 ~ 15 minutes in.
6. a kind of polycarbonate containing polyborosiloxane fire retardant prepared by the preparation method as described in claim any one of 1-5
Composite material, it is characterised in that: be prepared by weight by following component:
100 parts of polycarbonate,
0.5 ~ 2 part of polyborosiloxane fire retardant,
0.2 ~ 0.5 part of dispersing agent,
0.2 ~ 0.5 part of antioxidant.
7. polycarbonate composite material according to claim 6, it is characterised in that: the dispersing agent is organic silicon dispersion
Agent.
8. polycarbonate composite material according to claim 6, it is characterised in that: the antioxidant is β-(3,5- bis- uncles
Butyl -4- hydroxy phenyl) propionic acid n-octadecyl alcohol ester (anti-1076) and three [2,4- di-tert-butyl-phenyl] phosphite esters (resisting 168)
Compounding.
9. a kind of method for preparing polycarbonate composite material as claimed in claim 6, it is characterised in that: steps are as follows:
(1) by polycarbonate through 110 DEG C forced air drying 4 ~ 6 hours；
(2) by 100 parts of dry polycarbonate and 0.5 ~ 2 part of polyborosiloxane fire retardant in revolving speed be 200 ~ 300 revs/min
It is mixed 3 ~ 5 minutes in high-speed mixer；It is subsequently added into 0.2 ~ 0.5 part of dispersing agent, 0.2 ~ 0.5 part of antioxidant continuess to mix 3 ~ 5 points
Clock；
(3) material mixed is added twin-screw extrude into wire drawing and is granulated to obtain polycarbonate composite material；The twin-screw
The temperature of extruder is followed successively by 150 DEG C, 230 DEG C, 260 DEG C, 260 DEG C, 260 DEG C, 260 DEG C, 260 DEG C, 260 from feeding section to head
DEG C, 260 DEG C, 265 DEG C, screw diameter be 42 ~ 56 millimeters, screw slenderness ratio be 40 ~ 48.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410673776.XA CN105670259B (en) | 2014-11-21 | 2014-11-21 | A kind of polyborosiloxane fire retardant and the polycarbonate composite material and preparation method thereof containing polyborosiloxane fire retardant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410673776.XA CN105670259B (en) | 2014-11-21 | 2014-11-21 | A kind of polyborosiloxane fire retardant and the polycarbonate composite material and preparation method thereof containing polyborosiloxane fire retardant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105670259A CN105670259A (en) | 2016-06-15 |
| CN105670259B true CN105670259B (en) | 2019-02-22 |
Family
ID=56957510
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410673776.XA Active CN105670259B (en) | 2014-11-21 | 2014-11-21 | A kind of polyborosiloxane fire retardant and the polycarbonate composite material and preparation method thereof containing polyborosiloxane fire retardant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105670259B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106147603A (en) * | 2016-06-22 | 2016-11-23 | 安徽汇利涂料科技有限公司 | A kind of corrosion resistant water super-thin steel structure fire-proof paint |
| CN107083063B (en) * | 2016-10-20 | 2020-04-21 | 深圳市新纶科技股份有限公司 | Transparent flame-retardant organic silicon gel composition and preparation method thereof |
| CN109627729B (en) * | 2018-11-28 | 2021-01-08 | 宁波力达得为高分子科技有限公司 | Low-heat-release and low-smoke polycarbonate composite material |
| CN110511477A (en) * | 2019-09-26 | 2019-11-29 | 金发科技股份有限公司 | A kind of polypropylene ultralow linear expansion coefficient master batch and its application |
| CN110564129A (en) * | 2019-09-26 | 2019-12-13 | 金发科技股份有限公司 | Low-linear-expansion-coefficient flame-retardant polycarbonate composite material and preparation method thereof |
| CN114430066B (en) * | 2020-10-13 | 2023-10-31 | 中国石油化工股份有限公司 | Electrolyte and lithium ion battery containing same |
| CN113402714B (en) * | 2021-05-25 | 2022-10-11 | 长沙达菲新材料科技有限公司 | MarkIII type polycarbosilane and preparation method thereof |
| CN117285690A (en) * | 2023-09-15 | 2023-12-26 | 苏州易昇光学材料股份有限公司 | Flexible optical buffer material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5807953A (en) * | 1996-07-26 | 1998-09-15 | The United States Of America As Represented By The Secretary Of The Navy | Thermostet polymers from inorganic arylacetylenic monomers |
| US6180809B1 (en) * | 1996-02-29 | 2001-01-30 | L'etat Francais, Represente Par Le Delegue General Pour L'armement | Method of preparing silicon and boron oxynitrides |
| CN101965376A (en) * | 2008-03-04 | 2011-02-02 | 陶氏康宁公司 | Polyborosiloxane and method of preparing same |
| CN102250356A (en) * | 2011-06-20 | 2011-11-23 | 厦门大学 | Copolysilane and preparation method thereof |
| CN102775754A (en) * | 2012-07-25 | 2012-11-14 | 杭州师范大学 | Halogen-free composite flame retardant poly carbonates (PC)/acrylonitrile butadiene styrene copolymers (ABS) alloy and preparation method thereof |
| CN104086944A (en) * | 2014-07-24 | 2014-10-08 | 太仓市晨洲塑业有限公司 | Modified PC/ABS (Polycarbonate/Acrylonitrile Butadiene Styrene) alloy plastic |
-
2014
- 2014-11-21 CN CN201410673776.XA patent/CN105670259B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6180809B1 (en) * | 1996-02-29 | 2001-01-30 | L'etat Francais, Represente Par Le Delegue General Pour L'armement | Method of preparing silicon and boron oxynitrides |
| US5807953A (en) * | 1996-07-26 | 1998-09-15 | The United States Of America As Represented By The Secretary Of The Navy | Thermostet polymers from inorganic arylacetylenic monomers |
| CN101965376A (en) * | 2008-03-04 | 2011-02-02 | 陶氏康宁公司 | Polyborosiloxane and method of preparing same |
| CN102250356A (en) * | 2011-06-20 | 2011-11-23 | 厦门大学 | Copolysilane and preparation method thereof |
| CN102775754A (en) * | 2012-07-25 | 2012-11-14 | 杭州师范大学 | Halogen-free composite flame retardant poly carbonates (PC)/acrylonitrile butadiene styrene copolymers (ABS) alloy and preparation method thereof |
| CN104086944A (en) * | 2014-07-24 | 2014-10-08 | 太仓市晨洲塑业有限公司 | Modified PC/ABS (Polycarbonate/Acrylonitrile Butadiene Styrene) alloy plastic |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105670259A (en) | 2016-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105670259B (en) | A kind of polyborosiloxane fire retardant and the polycarbonate composite material and preparation method thereof containing polyborosiloxane fire retardant | |
| Zhang et al. | Preparation of lignin–silica hybrids and its application in intumescent flame-retardant poly (lactic acid) system | |
| CN105670258B (en) | A kind of high transparency halogen-free flameproof scratch resistant polycarbonate composite material and preparation method | |
| CN106147182B (en) | A kind of low fire-retardant scratch resistant polycarbonate composite material and preparation method of water suction | |
| Qian et al. | Thermal degradation and flammability of novel organic/inorganic epoxy hybrids containing organophosphorus-modified oligosiloxane | |
| CN108102213B (en) | Flame-retardant polypropylene composition and preparation method and application thereof | |
| CN100590145C (en) | Method for preparing high machinery performance halogen-free anti-flaming PBT composite and composite material | |
| CN105694414A (en) | High-content fiberglass-reinforced halogen-free flame-retardant PC (polycarbonate) composite and preparation method thereof | |
| CN101058669A (en) | Flame-proof thermoplastic polyurethane mixture containing halogen-free expanded fire retardant | |
| Jiang et al. | Polycarbonate composites flame‐retarded by polyphenylsilsesquioxane of ladder structure | |
| Peng et al. | Flame-retardant polyvinyl alcohol membrane with high transparency based on a reactive phosphorus-containing compound | |
| CN108752879A (en) | A kind of multiple-effect PBT modified plastics and preparation method | |
| CN104419161A (en) | Toughened and reinforced flame retardant polycarbonate and preparation method thereof | |
| CN103408914A (en) | Modified PC (polycarbonate) resin composite material used for household appliances and preparation method | |
| Niu et al. | Flame retardant bamboo fiber reinforced polylactic acid composites regulated by interfacial phosphorus-silicon aerogel | |
| CN101857692B (en) | PE/magnesium hydroxide composite flame retardant material | |
| CN115011078A (en) | Flame-retardant environment-friendly PET plastic and preparation method thereof | |
| CN110079073A (en) | CABLE MATERIALS of high flame resistance and preparation method thereof | |
| CN102649870A (en) | Halogen-free flame-retardant glass fiber reinforced PBT (polybutylece terephthalate) material | |
| CN110564129A (en) | Low-linear-expansion-coefficient flame-retardant polycarbonate composite material and preparation method thereof | |
| CN115850708A (en) | Preparation method and application of N-P-Si-containing cage polysilsesquioxane flame retardant | |
| CN107652520B (en) | Flame-retardant polyethylene product and preparation method thereof | |
| CN108410149A (en) | A kind of white polycarbonate composite material of Halogen-free flame retardant highlight porcelain | |
| CN107759749A (en) | Reaction-type flame-retarding vinyl ester resin of synergy and preparation method thereof | |
| CN103665798B (en) | A kind of automotive upholstery color inhibition PBT plastic and preparation 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |