CN1263786C - Phosphorus containing siloxane and process for preparing same - Google Patents
Phosphorus containing siloxane and process for preparing same Download PDFInfo
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- CN1263786C CN1263786C CN 200410068038 CN200410068038A CN1263786C CN 1263786 C CN1263786 C CN 1263786C CN 200410068038 CN200410068038 CN 200410068038 CN 200410068038 A CN200410068038 A CN 200410068038A CN 1263786 C CN1263786 C CN 1263786C
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Abstract
The present invention provides phosphorus containing polysiloxane and a preparation method thereof. The general chemical formula of the phosphorus containing polysiloxane is disclosed in the specifications. Firstly, a phosphoryl chloride compound is prepared from phosphorus oxychloride and diatomic alcohol as raw materials, and simultaneously, amino containing siloxane and low molecular weight hydroxy siloxane are copolymerized to obtain amino containing polysiloxane; secondly, the phosphoryl chloride compound and the amino containing polysiloxane are dissolved in an organic solvent and synthesized under the condition of temperature rise to obtain the phosphorus containing polysiloxane. The phosphorus containing polysiloxane as a flame retarding agent simultaneously containing various flame retarding elements, such as silicon, phosphorus, nitrogen, etc., is used in polyolefin, polyacrylic acid (ester), ABS, nylon, cellulose or polyvinyl alcohol. In the formula, R1 and R2 are respectively selected from CH3 or C6H5; R3 is selected from (CH2)r or (CH2)rNH(CH2)q; R4 and R5 are respectively selected from H, CH3 or C2H5.
Description
Technical field:
The present invention relates to a kind of fire-retardant organosilicon macromolecule material and preparation method thereof, particularly side chain phosphorated polysiloxane and preparation method thereof of being used for.
Background technology:
Silicoorganic compound have excellent biological compatibility, and permeability and low surface energy are very extensive to its research range; And, mainly concentrate on biological and fire-retardant aspect to the research of P contained compound.The common ground of these two kinds of elements is the flame retardant effects that can be used for improving polymkeric substance.In research in the past, the flame-retardant compound that they Chang Zuowei is different occurs.Along with the raising that can require Flame Retardancy, the flame-retardant compound that contains single-element more and more can not satisfy the requirement of application.To the exploitation of flame-retardant compound, concentrate on gradually on the mixture that uses multiple ignition-proof element simultaneously.Expansion type flame retardant is exactly wherein a kind of composite fire retardant.It is generally by acid source, and charcoal source and source of the gas are formed, and have flame retardant effect preferably.But the consistency of they and polymkeric substance, particularly polyolefins is poor, is subjected to certain restriction on using.And the three elements in the expansion type flame retardant are usually from different compounds, and this makes the distribution of three elements in polymkeric substance be difficult to evenly, thereby influences flame retardant properties.(J Appl Polym Sci 2000 such as Taiwan's scholars Hsiue GingHo in recent years; 78:1～8) group that contains organic silicon group and phosphoric respectively is introduced directly in the Resins, epoxy molecular structure, finds that silicon and phosphorus can provide collaborative fire retardation for polymkeric substance in same polymkeric substance.But in this reactive minority polymkeric substance of introducing suitable Resins, epoxy only.
Summary of the invention:
The objective of the invention is to synthesize a kind of phosphorus containing siloxane that contains phosphoric and element silicon simultaneously, the three elements and the organosilicon radical of expansion type flame retardant are connected together by chemical bond-linking, prepare a kind of new phosphorus containing siloxane, this not only can overcome expansion type flame retardant and distribute uneven problem in polymkeric substance, simultaneously can also be by the synergistic effect of phosphorus and silicon, for polymkeric substance provides better flame retardant effect.
The repeated structural unit of phosphorus containing siloxane of the present invention is as follows:
R
1, R
2Be selected from CH respectively
3Or C
6H
5
R
3Be selected from (CH
2)
rOr (CH
2)
rNH (CH
2)
q
R
4, R
5Be selected from H respectively, CH
3Or C
2H
5
Wherein, m=1～40, n=1～20, p=20～200, r, q are 1～5 integer.
The concrete preparation method of a kind of phosphorus containing siloxane of the present invention is as follows:
(a) the 1mol dibasic alcohol is joined in 100～1000ml organic solvent, stir rising temperature for dissolving, controlled temperature is at 0～80 ℃ then, add 1.0～2.0mol phosphorus oxychloride, stir, reflux, with the gaseous by-product in the basic solution absorption reaction, reacted 1～20 hour, distillation removes and desolvates and unreacted reactant then, uses the organic solvent wash products, suction filtration, drying is 1～10 hour in vacuum drying oven, obtains the phosphoryl chloride compound;
(b) 1mol is contained amino organoalkoxysilane, 0.1～2mol water and 0.001～0.02mol catalyzer at room temperature mix, under nitrogen environment, be warming up to 50～130 ℃, reacted 8～100 hours, after reaction finished, unreacted reactant and water were removed in underpressure distillation, obtained containing the hydrolysate of amino organoalkoxysilane;
(c) 1mol is contained the hydrolysate of amino organoalkoxysilane and the α of 0.1～10mol, ω dihydroxyl siloxanes is mixed, add 0.01～0.2mol water, 0.001～0.02mol catalyzer is warming up to 90～130 ℃, reacts 1～10 hour, controlled temperature is 140～180 ℃ of successive reactions 1～8 hour more then, cool to 110 ℃ then, decompression dewatered 1～10 hour, obtained containing amino polysiloxane;
(d) 0.1～1mol phosphoryl chloride compound and 1～0.1mol being contained amino polysiloxane is dissolved in respectively in 30～1000ml organic solvent, the solution of phosphoryl chloride compound is joined in the polysiloxane solution, control reaction temperature is at 20～50 ℃, reacted 1～10 hour, after reaction is finished, remove and desolvate, obtain phosphorus containing siloxane.
The entire reaction equation of phosphorus containing siloxane preparation of the present invention can be expressed as:
The chemical structural formula of the dibasic alcohol that the present invention adopts is as follows:
R
4, R
5Be selected from H respectively, CH
3Or C
2H
5
The chemical structural formula that contains amino organoalkoxysilane that the present invention adopts is as follows:
R
3Be selected from (CH
2)
rOr (CH
2)
rNH (CH
2)
q
R
6, R
7Be selected from OCH respectively
3Or OC
2H
5
R, q are 1～5 integer.
The α that the present invention adopts, the chemical structural formula of ω dihydroxyl siloxanes is as follows:
R
1, R
2Be selected from CH respectively
3Or C
6H
5N=1～20.
The organic solvent that the present invention adopts has benzene, toluene, dimethylbenzene, chloroform, methylene dichloride, acetone, tetracol phenixin, dehydrated alcohol, ether or tetrahydrofuran (THF).
The catalyzer that the present invention adopts has potassium hydroxide, sodium hydroxide, the vitriol oil or Tetramethylammonium hydroxide.
The side chain phosphorus containing siloxane that the present invention obtains can be applied to polyolefine, polyacrylic acid (ester), ABS, in the nylon as fire retardant.Compare with traditional fire retardant, it is not halogen-containing, has the three elements of expansion type flame retardant simultaneously, so this fire retardant is applied in the polymkeric substance, not only has good processing properties, also has good flame retardancy.
Description of drawings:
Fig. 1 is the infrared spectra of embodiment 1 phosphoryl chloride compound;
Fig. 2 is the infrared spectra that contains amino polysiloxane among the embodiment 1;
Fig. 3 is the infrared spectra of phosphorus containing siloxane among the embodiment 1;
Embodiment:
The present invention will be described in more details technical scheme of the present invention by the following specific embodiments, but the present invention is not limited to embodiment proposed below.
Embodiment 1:
(a) take by weighing the 1mol neopentyl glycol, join in the 300ml chloroform, stir rising temperature for dissolving.Controlled temperature drips the 1mol phosphorus oxychloride at 0 ℃ then.Drip phosphorus oxychloride, be warmed up to 20 ℃, and kept 4 hours in this temperature.Remove chloroform, the product benzene that obtains, CCl
4, dehydrated alcohol cleans respectively 3 times, puts into 80 ℃ of baking ovens dry about 10 hours, obtains the phosphoryl chloride compound.Accompanying drawing 1 is the infrared spectrogram of phosphoryl chloride compound: FTIR (KBr, cm
-1): 2896～2975 (CH
2-,-CH
3); 1304 (P=O); 1000～1100 (P-O-C); 540 (P-Cl).
(b) (r=3, q=2) 1mol add entry 2mol, and potassium hydroxide 0.01mol is warmed up to 80～100 ℃, and under nitrogen protection, constant temperature 12 hours removes and anhydrates, and obtains the hydrolysate of aminosilane to take by weighing the siloxanes that contains amino.
(c) take by weighing the hydrolysate of 0.5mol aminosilane and the α of 0.5mol, (R1, R2 is CH to the alpha, omega-dihydroxy dimethyl siloxane
3, n=4) mixed, add entry 1mol, Tetramethylammonium hydroxide 0.001mol, under nitrogen protection, temperature is controlled at 110 ℃, stirs 10 hours, obtain containing amino polysiloxane (molecular weight is 110,000, m=4, n=4, p=118).Accompanying drawing 2 is for containing the infrared spectra of amino polysiloxane: FTIR (KBr, cm
-1): 3200～3340 (NH
2,-NH-); 2884-2963 (CH
2-,-CH
3); 1260 (Si-O); 1000～1100 (Si-O-Si); 800 (Si-C).
(d) take by weighing 0.1mol phosphoryl chloride compound respectively, the 0.1mol amino silicones is dissolved in respectively in the 50ml chloroform.The phosphoryl chloride compound solution is slowly joined in the amino silicones solution, and control reaction temperature is at 30 ℃.After 3 hours, remove and to desolvate, obtain phosphorus containing siloxane (wherein, m=4, n=4, p=118, r=3, q=2).Accompanying drawing 3 is the infrared spectra of this phosphorus containing siloxane: FTIR (KBr, cm
-1): 3400 (NH-); 2884-2963 (CH
2-,-CH
3); 1260 (Si-O, P=O); 1235 (P=O); 1000～1100 (Si-O-Si, P-O-C); 800 (Si-C).
Embodiment 2:
(a) take by weighing the 1mol neopentyl glycol, join in the 300ml chloroform, stir rising temperature for dissolving.Controlled temperature drips the 1mol phosphorus oxychloride at 0 ℃ then.Drip phosphorus oxychloride, be warmed up to 20 ℃, and kept 4 hours in this temperature.Remove chloroform, the product that obtains cleans 3 times with dehydrated alcohol, puts into 80 ℃ of baking ovens about 10 hours, obtains the phosphoryl chloride compound.
(b) (r=3, q=2) 1mol add entry 2mol, and potassium hydroxide 0.01mol is warmed up to 80～100 ℃, and under nitrogen protection, constant temperature 12 hours removes and anhydrates, and obtains the hydrolysate of aminosilane to take by weighing the siloxanes that contains amino.
(c) take by weighing the hydrolysate of 0.5mol aminosilane and the α of 0.5mol, (R1, R2 is CH to the alpha, omega-dihydroxy dimethyl siloxane
3) and the another kind of α of 0.5mol, (R1, R2 is C to the alpha, omega-dihydroxy dimethyl siloxane
6H
5) mixed, add entry 2mol, Tetramethylammonium hydroxide 0.001mol, nitrogen protection, temperature is controlled at 110 ℃, stirs 10 hours, obtain containing amino polysiloxane (m=2, n=2, p=80).
(d) take by weighing 0.2mol phosphoryl chloride compound respectively, the 0.2mol amino silicones is dissolved in respectively in the 50ml chloroform.Phosphoryl chloride solution is slowly joined in the amino silicones solution, and control reaction temperature is at 30 ℃.After 3 hours, remove and to desolvate, obtain phosphorus containing siloxane (wherein, m=2, n=2, p=80, r=3, q=2).
Embodiment 3:
According to the phosphorus containing siloxane fire retardant 30g that embodiment 1 obtains, it is mixing even that polypropylene 70g puts into Banbury mixer, and melting temperature is 170 ℃, and mixing time is 8 minutes, obtains polypropylene flame redardant.Its oxygen index is 27.0, and at 800 ℃ of very high charring rates of acquisition (in the nitrogen is: 27%; In the air be: 12%; In the oxygen be: 13%).
Claims (7)
1. phosphorus containing siloxane is characterized in that its repeating unit is shown below:
R
1, R
2Be selected from CH respectively
3Or C
6H
5
R
3Be selected from (CH
2)
rOr (CH
2)
rNH (CH
2)
q
R
4, R
5Be selected from H respectively, CH
3Or C
2H
5
Wherein, m=1～40, n=1～20, p=20～200, r, q are 1～5 integer.
2. the preparation method of the described phosphorus containing siloxane of claim 1 is characterized in that the preparation method is as follows:
(a) the 1mol dibasic alcohol is joined in 100～1000ml organic solvent, stir rising temperature for dissolving, controlled temperature is at 0～80 ℃ then, add 1.0～2.0mol phosphorus oxychloride, stir, reflux, with the gaseous by-product in the basic solution absorption reaction, reacted 1～20 hour, distillation removes and desolvates and unreacted reactant then, uses the organic solvent wash products, suction filtration, drying is 1～10 hour in vacuum drying oven, obtains the phosphoryl chloride compound;
(b) 1mol is contained amino organoalkoxysilane, 0.1～2mol water and 0.001～0.02mol catalyzer at room temperature mix, under nitrogen environment, be warming up to 50～130 ℃, reacted 8～100 hours, after reaction finished, unreacted reactant and water were removed in underpressure distillation, obtained containing the hydrolysate of amino organoalkoxysilane;
(c) 1mol is contained the hydrolysate of amino organoalkoxysilane and the α of 0.1～10mol, ω dihydroxyl siloxanes is mixed, add 0.01～0.2mol water, 0.001～0.02mol catalyzer is warming up to 90～130 ℃, reacts 1～10 hour, controlled temperature is 140～180 ℃ of successive reactions 1～8 hour more then, cool to 110 ℃ then, decompression dewatered 1～10 hour, obtained containing amino polysiloxane;
(d) 0.1～1mol phosphoryl chloride compound and 1～0.1mol being contained amino polysiloxane is dissolved in respectively in 30～1000ml organic solvent, the solution of phosphoryl chloride compound is joined in the polysiloxane solution, control reaction temperature is at 20～50 ℃, reacted 1～10 hour, after reaction is finished, remove and desolvate, obtain phosphorus containing siloxane.
3. the preparation method of phosphorus containing siloxane according to claim 2 is characterized in that the chemical structural formula of dibasic alcohol is as follows:
R
4, R
5Be selected from H respectively, CH
3Or C
2H
5
4. the preparation method of phosphorus containing siloxane according to claim 2, the chemical structural formula that it is characterized in that containing amino organoalkoxysilane is as follows:
R
3Be selected from (CH
2)
rOr (CH
2)
rNH (CH
2)
q
R
6, R
7Be selected from OCH respectively
3Or OC
2H
5
R, q are 1～5 integer.
5. the preparation method of phosphorus containing siloxane according to claim 2 is characterized in that α, and the chemical structural formula of ω dihydroxyl siloxanes is as follows:
R
1, R
2Be selected from CH respectively
3Or C
6H
5N=1～20.
6. the preparation method of phosphorus containing siloxane according to claim 2 is characterized in that organic solvent has benzene, toluene, dimethylbenzene, chloroform, methylene dichloride, acetone, tetracol phenixin, dehydrated alcohol, ether or tetrahydrofuran (THF).
7. the preparation method of phosphorus containing siloxane according to claim 2 is characterized in that catalyzer has potassium hydroxide, sodium hydroxide, the vitriol oil or Tetramethylammonium hydroxide.
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|---|---|---|---|
| CN 200410068038 CN1263786C (en) | 2004-11-11 | 2004-11-11 | Phosphorus containing siloxane and process for preparing same |
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|---|---|---|---|
| CN 200410068038 CN1263786C (en) | 2004-11-11 | 2004-11-11 | Phosphorus containing siloxane and process for preparing same |
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| CN1263786C true CN1263786C (en) | 2006-07-12 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106700081A (en) * | 2017-01-22 | 2017-05-24 | 太原理工大学 | Polysiloxane fire retardant containing nitrogen, phosphorus and silicon, and preparation method thereof |
| CN106700081B (en) * | 2017-01-22 | 2020-04-07 | 太原理工大学 | Polysiloxane flame retardant containing nitrogen, phosphorus and silicon and preparation method thereof |
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