CN106832297A - The linear copolymer of a kind of main chain containing DDSQ and ODOPN structures and its preparation method and application - Google Patents
The linear copolymer of a kind of main chain containing DDSQ and ODOPN structures and its preparation method and application Download PDFInfo
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- CN106832297A CN106832297A CN201710177515.2A CN201710177515A CN106832297A CN 106832297 A CN106832297 A CN 106832297A CN 201710177515 A CN201710177515 A CN 201710177515A CN 106832297 A CN106832297 A CN 106832297A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/30—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen phosphorus-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
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- Chemical Kinetics & Catalysis (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
Linear copolymer the present invention relates to the miscellaneous luxuriant and rich with fragrance ODOPN structures of a kind of DDSQ containing polysiloxane and phosphinylidyne and preparation method thereof, preparation method comprises the following steps：(1) by ODOPN, Carbon Dioxide caesium and solvent are mixed, and add bromopropene or propargyl bromide temperature rising reflux overnight, isolated white powdery solids.(2) mixing of white powdery solids, DDSQ, solvent and catalyst is warming up to the boiling point of solvent under nitrogen protection, 18~30h of back flow reaction, rotary evaporation removes reacted organic solvent, obtains final product required copolymer.The linear copolymer containing DDSQ and ODOPN structures that the present invention is obtained can be used as fire retardant, and this kind of fire retardant, raw material is simple and easy to get, heat endurance is high, suitable for PC/ABS alloys, with phosphorus silicon cooperative flame retardant effect, addition is only that 10wt% can reach flame-retardancy requirements.
Description
Technical field
The present invention relates to engineering plastics flame retardant area, and in particular to a kind of efficient novel phosphorus-silicon linear copolymer of Halogen
Fire retardant, the fire retardant has and prepares simple, and raw material is easy to get, good flame retardation effect, the advantages of Halogen is nontoxic, can be added to PC/ABS
Alloy is used as flame-retardant additive.
Background technology
Miscellaneous -10- phospho hetero phenanthrenes -10- the oxides (DOPO) of 9,10- dihydro-9-oxies are a kind of new organophosphorous fire retardants.
ODOPN is that DOPO and naphthoquinones carry out addition reaction and obtain such as formula 1, and ODOPN has heat resistance higher, relatively low hygroscopicity and water
Xie Xing, can serve as fire-retardant intermediate.Contain two phenolic hydroxyl groups in ODOPN molecules, can be reacted with bromopropene or propargyl bromide, generation
ODOPN derivative of the two ends with unsaturated bond.
Formula 1
Multiaspect cage type silsesquioxane is a kind of organic-inorganic nano hybrid structure interesting in recent years, frequently as modified
Agent or comonomer are used for modified polymer material.Double-deck silsesquioxane (DDSQ) is the more polysiloxanes of research,
Because of its molecule nano level size, regular cage structure and excellent organic compatibility, catabolite can be in polymerization under high temperature
Thing surface forms silica diaphragm, is widely used in the fire-retardant neighborhood of macromolecular material.In addition, DDSQ contains two activated silica hydrogen
Key, can carry out hydrosilylation with unsaturated bond, for synthesizing linear copolymer fire retardant.
In order to construct the polymer containing element silicon and P elements, using the synergy between phosphorus and silicon, polymerization is improved
The flame retardant effect of thing.Unsaturated compound of the present invention with polysiloxanes DDSQ and containing ODOPN structures is added as raw material by silicon hydrogen
Into reaction, prepare a kind of novel phosphorus-silicon linear copolymer fire retardant, and be applied to PC/ABS alloys it is fire-retardant in, improve and close
The fire resistance of gold, it is to avoid halogen-containing materials pollute environment.
The content of the invention
Polysiloxanes DDSQ is obtained one by the technical problems to be solved by the invention with the copolymer compound containing ODOPN structures
Kind new linear copolymer fire retardant with phosphorus silicon cooperative effect, the fire retardant heat endurance is high, environmentally friendly, Halogen without
Poison, flame retarding efficiency is high.
The linear copolymer fire retardant of a kind of new DDSQ containing polysiloxane and ODOPN structures, chemical structural formula such as formula 2
It is shown：
Formula 2
R in the formula 2=Or, n is 8~10 integer.
A kind of linear copolymer fire retardant of new DDSQ containing polysiloxane and ODOPN structures, preparation method is included such as
Lower step：
(1) by ODOPN, Carbon Dioxide caesium and solvent are added in the round-bottomed flask with stirrer, add the crown- of catalyst 18
6,6 h are stirred at room temperature, add bromopropene（Or propargyl bromide）Overnight, depressurize temperature rising reflux suction filtration after the completion of reaction, and filtrate is spin-dried for, post
Isolated white powdery solids a（Or b）；
The structural formula of the ODOPN is：。
(2) white powdery solids a is sequentially added in the three-neck flask with stirrer（Or b）, DDSQ（Double-deck times
Half siloxanes, synthetic method is shown in the 3473-3475. of Macromolecules 39 (2006)）, nitrogen protection is lower add solvent with
And catalyst, the boiling point of solvent is progressively warming up to, the h of back flow reaction 18~30, rotary evaporation removes reacted organic solvent,
Normal temperature is down to, gray solid as novel phosphorus-silicon copolymer is obtained；
The structural formula of the DDSQ is：。
In step (1), the solvent is acetonitrile, acetone, methyl alcohol, any one in DMF, the ODOPN, bromopropene
（Propargyl bromide）, the ratio between the amount of cesium carbonate material and 18 crown-s 6 is 1：3.0-6.0：2.0-5.0：0.02.
In step (2), the solvent is any one in THF, toluene, DMF, benzene, the DDSQ and compound a（b）
The amount ratio of material is 1：0.8~2, catalyst is 15/1000000ths~35 times of reactant gross mass, and the catalyst is
Karstedt catalyst.
It is as follows that a kind of new linear copolymer fire retardant containing polysiloxane and ODOPN structures prepares reaction equation：
The linear copolymer of the new DDSQ containing polysiloxane for preparing and ODOPN structures is added in PC/ABS as phosphorus silicon
Synergistic fire retardant.
Compared with prior art, the invention has the advantages that：
The present invention obtains the linear copolymer fire retardant of a kind of new DDSQ containing polysiloxane and ODOPN structures, this kind of fire-retardant
Agent, raw material is simple and easy to get, and heat endurance is high, it is adaptable to PC/ABS alloys, and with phosphorus silicon cooperative flame retardant effect, addition is only
10wt% is that can reach flame-retardancy requirements.
Specific embodiment
The invention will be further described with reference to embodiments, but the claimed scope of the invention is not limited to implement
Example express ranges.
Case study on implementation 1
ODOPN（Laboratory is made by oneself, and method is shown in Hubei University (Natural Science)） 36 (2014) 351-
354.）（1.12g, 3 mmol）, Carbon Dioxide caesium（2.93 g, 15 mmol）Add in the mono- neck flasks of 50 mL, add acetonitrile
(20 mL) and 18 crown-s 6（15.8 mg, 0.06 mmol）, the h of stirring at normal temperature 6, addition bromopropene（1.25 mL, 15 mmol）,
80 DEG C of 12 h of reaction, are cooled to room temperature, and suction filtration, filtrate is spin-dried for, dichloromethane petroleum ether post separation, obtain white solid, and vacuum is done
Dry 12 h, obtains ODOPN derivatives a (1.08 g, 80%).DDSQ is added in the reactor with stirrer（Method is referred to
The 3473-3475. of document Macromolecules 39 (2006)））(3.0 g, 2.61 mmol), derivative a (1.14 g,
2.58 mmol), anhydrous THF (50 mL), nitrogen protection is lower to add 60 uL karstedt catalyst, after 30 min of stirring, 60
36 h are reacted under the conditions of DEG C makes reaction complete；Vacuum distillation removes solvent after the completion of reaction, is recrystallized to give gray solid and is
Copolymer I（N is the integer of 8-10）(3.30g, 79.8%).1H NMR (ppm, CDCl3): 0.23 (6H, CH3-Si),
0.33 (4H, -CH2- Si), 2.0 (4H ,-CH2-CH2-O-Ph), 4.83 (4H, -CH2-O-Ph), 6.35-8.0 (m,
112H, phenyl ring)；31P NMR (ppm, CDCl3)：21.25-22.18；29Si NMR (ppm, CDCl3): -35.80, -
75.73 and -76.76.
Case study on implementation 2
ODOPN（1.12g, 3 mmol）, Carbon Dioxide caesium（2.35 g, 1.2 mmol）Add in the mono- neck flasks of 50 mL, add
Acetonitrile (20 mL) and 18 crown-s 6（15.8 mg, 0.06 mmol）, the h of stirring at normal temperature 6, addition bromopropene（1.0 mL, 1.2
mmol）, 80 DEG C are reacted 12 h, are cooled to room temperature, and suction filtration, filtrate is spin-dried for, dichloromethane petroleum ether post separation, obtains white solid,
12 h are vacuum dried, ODOPN derivatives a (1.02 g, 75.6%) is obtained.DDSQ is added in the reactor with stirrer
(3.0 g, 2.61 mmol), derivative a (1.14 g, 2.58 mmol), dry toluene (50 mL), nitrogen protection is lower to be added
60 uL karstedt catalyst, after 30 min of stirring, 36 h are reacted under the conditions of 110 DEG C makes reaction complete；Subtract after the completion of reaction
Pressure is distilled off solvent, is recrystallized to give gray solid as copolymer I（N is the integer of 8-10）（2.04 g, 65%）.
Case study on implementation 3
ODOPN（1.12g, 3 mmol）, Carbon Dioxide caesium（2.93 g, 15 mmol）Add in the mono- neck flasks of 50 mL, add
Acetonitrile (20 mL) and 18 crown-s 6（15.8 mg, 0.06 mmol）, the h of stirring at normal temperature 6, addition propargyl bromide（1.0 mL, 12
mmol）, 80 DEG C are reacted 12 h, are cooled to room temperature, and suction filtration, filtrate is spin-dried for, dichloromethane petroleum ether post separation, obtains white solid,
12 h are vacuum dried, ODOPN derivatives b (1.08 g, 80%) is obtained.DDSQ is added in the reactor with stirrer
(3.0 g, 2.61 mmol), derivative b (1.14 g, 2.58 mmol), anhydrous THF (50 mL), nitrogen protection is lower to be added
60 uL karstedt catalyst, after 30 min of stirring, 36 h are reacted under the conditions of 60 DEG C makes reaction complete；Subtract after the completion of reaction
Pressure is distilled off solvent, is recrystallized to give gray solid as copolymers II（N is the integer of 8-10）(3.64 g, 88%).1H
NMR (ppm, CDCl3): 0.23 (6H, CH3-Si), 0.33 (4H, -CH2-Si), 4.23 (4H, -CH2-O-Ph),
5.56 (2H ,-CH=), CH-O-Ph 6.35-8.0 (m, 96H, phenyl ring)；31P NMR (ppm, CDCl3)：21.35-24.44
；29Si NMR (ppm, CDCl3):- 46.81, -77.73 and -78.82.
Case study on implementation 4
ODOPN（1.12g, 3 mmol）, Carbon Dioxide caesium（2.93 g, 15 mmol）Add in the mono- neck flasks of 50 mL, add
Acetonitrile (20 mL) and 18 crown-s 6（15.8 mg, 0.06 mmol）, the h of stirring at normal temperature 6, addition propargyl bromide（1.25 mL, 15
mmol）, 80 DEG C are reacted 12 h, are cooled to room temperature, and suction filtration, filtrate is spin-dried for, dichloromethane petroleum ether post separation, obtains white solid,
12 h are vacuum dried, ODOPN derivatives b (1.14 g, 84.44%) is obtained.DDSQ is added in the reactor with stirrer
(3.0 g, 2.61 mmol), derivative b (1.14 g, 2.58 mmol), dry toluene (50 mL), nitrogen protection is lower to be added
60 uL karstedt catalyst, after 30 min of stirring, 36 h are reacted under the conditions of 110 DEG C makes reaction complete；Subtract after the completion of reaction
Pressure is distilled off solvent, is recrystallized to give gray solid as copolymers II（N is the integer of 8-10） (2.90 g, 70%).
The present invention is provided during novel phosphorus-silicon fire retardant is added to PC/ABS alloys and applies as follows：
Flame retardant test uses Vertical combustion instrument and limited oxygen index instrument, is tested according to respective standard.
Shown in fire resistance test data table 1 below：
From upper table it will be seen that using phosphorus silicon linear copolymer fire retardant of the invention, alloy fire resistance is obviously improved,
And fire retardant I is identical with effect with fire retardant II.When flame retardant amount reaches 10%, fire retardation PC/ABS LOI values can increase to
More than 27.0%, UL-94 reach V0 grades, substantially meet PC/ABS and apply needs.
Above description is only preferable case study on implementation of the invention, is not intended to limit the invention.Clearly for this area
Professional for, after present disclosure and principle is understood, all may be without departing substantially from the principle of the invention, the situation of structure
Under, the various modifications and change in form and details are carried out, but these modifications and change are still in claimed scope of the invention
Within.
Claims (6)
1. a kind of main chain contains the linear copolymer of DDSQ and ODOPN structures, and its chemical structural formula is shown below：
R in formula=Or, n is 8~10 integer.
2. main chain described in claim 1 contains the preparation method of the linear copolymer of DDSQ and ODOPN structures, including following step
Suddenly：
(1) by ODOPN, Carbon Dioxide caesium and organic solvent are added in the round-bottomed flask with stirrer, add 18 crown-s 6,
6 h are stirred at room temperature, bromopropene or propargyl bromide temperature rising reflux is added overnight, depressurize suction filtration after the completion of reaction, and filtrate is spin-dried for, post separation
Obtain white powdery solids compound a or b；
The structural formula of the ODOPN is：；
(2) white powdery solids compound a or b are sequentially added in the three-neck flask with stirrer, DDSQ, nitrogen is protected
Shield is lower to add organic solvent and catalyst, is progressively warming up to the boiling point of organic solvent, and the h of back flow reaction 18~30, rotation is steamed
Hair removes reacted organic solvent, is down to normal temperature, obtains gray solid and is DDSQ containing polysiloxane and ODOPN structures
Linear copolymer
The structural formula of the DDSQ is：。
3. preparation method according to claim 2, it is characterised in that：The catalyst is karstedt catalyst.
4. preparation method according to claim 2, it is characterised in that：In step (1), the solvent be acetonitrile, acetone,
The ratio between amount of methyl alcohol, any one in DMF, the ODOPN, bromopropene or propargyl bromide, cesium carbonate and the material of 18 crown- 6 is 1：
3.0-6.0：2.0-5.0：0.02；In step (2), the solvent is any one in THF, toluene, DMF, benzene, the DDSQ
It is 1 with the amount ratio of compound a or b materials：0.8~2, catalyst is 15/1000000ths~35 times of reactant gross mass.
5. main chain described in claim 1 contains the linear copolymer of DDSQ and ODOPN structures as the application of fire retardant.
6. application according to claim 5, it is characterised in that：The fire retardant is that main chain is contained into DDSQ and ODOPN knots
The linear copolymer of structure is added in PC/ABS alloys as flame-retardant additive.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110982282A (en) * | 2019-12-26 | 2020-04-10 | 陈志强 | Fluorosilicone rubber composition and preparation method thereof |
| CN114752337A (en) * | 2022-05-12 | 2022-07-15 | 江苏瑞洋安泰新材料科技有限公司 | Waterproof MS sealant and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492171A (en) * | 2011-11-11 | 2012-06-13 | 上海交通大学 | Novel phosphorous siliciferous flame retardant and preparation method thereof |
| CN103819634A (en) * | 2014-01-28 | 2014-05-28 | 厦门大学 | Block copolymer containing phosphorus and silicon and preparation method of block copolymer |
| CN104725667A (en) * | 2015-03-10 | 2015-06-24 | 三峡大学 | Novel phosphorus and silicon flame retardant with double caged phosphate structure as well as preparation method and application of novel flame retardant |
-
2017
- 2017-03-23 CN CN201710177515.2A patent/CN106832297A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492171A (en) * | 2011-11-11 | 2012-06-13 | 上海交通大学 | Novel phosphorous siliciferous flame retardant and preparation method thereof |
| CN103819634A (en) * | 2014-01-28 | 2014-05-28 | 厦门大学 | Block copolymer containing phosphorus and silicon and preparation method of block copolymer |
| CN104725667A (en) * | 2015-03-10 | 2015-06-24 | 三峡大学 | Novel phosphorus and silicon flame retardant with double caged phosphate structure as well as preparation method and application of novel flame retardant |
Non-Patent Citations (1)
| Title |
|---|
| 宋文朋等: ""双层倍半硅氧烷与DOPO衍生物线性共聚物的合成及表征"", 《胶体与聚合》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110982282A (en) * | 2019-12-26 | 2020-04-10 | 陈志强 | Fluorosilicone rubber composition and preparation method thereof |
| CN114752337A (en) * | 2022-05-12 | 2022-07-15 | 江苏瑞洋安泰新材料科技有限公司 | Waterproof MS sealant and preparation method thereof |
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