CN114031779B - Phosphorus-containing ladder-shaped polysiloxane, preparation method thereof and application of phosphorus-containing ladder-shaped polysiloxane as flame-retardant synergist - Google Patents
Phosphorus-containing ladder-shaped polysiloxane, preparation method thereof and application of phosphorus-containing ladder-shaped polysiloxane as flame-retardant synergist Download PDFInfo
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Abstract
The invention provides a phosphorus-containing ladder-shaped polysiloxane, a preparation method thereof and application thereof as a flame-retardant synergist, wherein phenyl trialkoxysilane and phosphorus-containing trialkoxysilane are mixed and dissolved in toluene, hydrochloric acid is slowly added, the reaction is carried out for 5 to 15 hours at normal temperature, the mixture is taken out and washed to be neutral, and an organic phase is dried; heating the organic phase mixture to 60-90 ℃, adding potassium hydroxide-methanol solution as a catalyst, performing reflux reaction to obtain a mixture with white precipitates, filtering insoluble substances, drying the filtrate, and evaporating the solvent to obtain a white solid product. According to the invention, the high-efficiency carbon formation is realized by introducing the phenyl group, the melting point of the polysiloxane is improved, the organosilicon modifier and the synergist are prevented from existing in a liquid state under common use conditions, and the precipitation phenomenon is avoided. By introducing the glycerol phosphate unit, the flame retardant property is enhanced through the carbon forming effect of the phosphate at a high temperature stage.
Description
Technical Field
The invention belongs to the technical field of polymer chemistry, relates to a phosphorus-containing ladder-shaped siloxane, and particularly relates to a phosphorus-containing ladder-shaped polysiloxane, a preparation method thereof and application thereof as a flame-retardant synergist.
Background
The glass fiber reinforced polyamide flame-retardant modified material is widely applied to electronic and electrical applications such as electrical shells, fuse boxes, switches and the like in the industries of automobiles and household appliances. Along with the application and popularization of new energy automobiles, the flame retardant requirements of charging piles and automobile electrical parts are increasing day by day. In order to ensure the compliance and the safety, a flame retardant is required to be added into the formula. In view of the safety of the combustion products, halogen-free flame retardant additive solutions are increasingly favored by modifying manufacturers and customers. The flame retardant such as diethyl aluminum hypophosphite developed by the Clariant company can achieve excellent flame retardant performance when being compounded with melamine polyphosphate, but some typical problems exist at present, such as the following:
1) The addition amount is higher, and the use amount is generally 18-20% to reach the standard;
2) The mechanical property of the flame-retardant nylon material is greatly reduced due to the higher addition amount;
3) The apparent pH value of the melamine polyphosphate is between 4 and 5, the melamine polyphosphate has more obvious acidity at high temperature, and the aging of nylon is accelerated and processing equipment is corroded;
4) The flowability is poor, and the trafficability of a workpiece formed by a thin wall or with a complex geometric shape is poor during injection molding;
the problems can be solved or partially solved by introducing different synergists, for example, by introducing aluminum phosphite, and adopting a compound of diethyl aluminum hypophosphite and aluminum phosphite, MPP can be replaced, and the acidic corrosion and the degradation of a flame retardant are reduced, but the addition amount is still more than 18%; foreign companies develop systems such as Safire 400 (melamine-zinc ion mixed polyphosphate) and the like, and when the amount of the system is 15%, the system can achieve 0.8mm V-0 flame retardance, but the color of a product is grayish and the color matching is difficult to achieve; the product Amgard PA1 which can replace MPP is developed by Solvay company, is a calcium ion-melamine-containing polyphosphate system, has a near-neutral apparent pH value, can reduce the corrosion of a flame retardant to equipment, and has no reduction of the addition amount when being used together with aluminum diethylhypophosphite. Dow corning proposed a series of silicon synergists, such as phenyl silicone oil systems 40-001, 43-821, etc., which can be used in combination with aluminum diethylphosphinate systems, but the flame retardant performance of products with the thickness of less than 1.0mm is not stable.
Therefore, the present invention is to solve the above problems, and an object thereof is to:
1) Introducing phenyl silicon units: the high-efficiency carbon formation is realized by introducing phenyl groups, the melting point of polysiloxane is improved, and the phenomenon that organic silicon modifiers and synergists exist in a liquid state under common use conditions and have precipitation risk is avoided;
2) And introducing a glycerol phosphate unit, and enhancing the flame retardant property through the carbon forming effect of phosphate at a high temperature stage, so as to realize the application in the thin products.
Disclosure of Invention
In order to achieve the purpose, the invention provides a phosphorus-containing ladder-shaped polysiloxane used as a flame-retardant synergist, wherein the structural formula of the phosphorus-containing ladder-shaped polysiloxane is as follows:
in the formula:
is a repeating group of a plurality of groups,
the phosphorus-containing ladder siloxane is ladder-shaped polysiloxane with hydroxyl as terminal group
R is R 1 Or R 2 Wherein R is 1 Is phenyl, R 2 Is composed of
The invention also aims to provide a preparation method of the phosphorus-containing ladder-shaped polysiloxane, which specifically comprises the following steps:
s1, mixing and dissolving phenyl trialkoxysilane and phosphorus-containing trialkoxysilane in toluene, slowly adding hydrochloric acid, reacting at normal temperature for 5-15 hours, taking out, washing to be neutral, and drying an organic phase;
s2, heating the organic phase mixture to 60-90 ℃, adding a potassium hydroxide-methanol solution as a catalyst, performing reflux reaction to obtain a mixture with white precipitates, filtering insoluble substances, drying the filtrate, and evaporating the solvent to obtain a white solid product.
In S1, the phenyltrialkoxysilane can be one or a mixture of more than two of commercially available phenyltrimethoxysilane, phenyltriethoxysilane and phenyltriisopropoxysilane.
Preferably, in S1, the phosphorus-containing trialkoxysilane is synthesized by the following method:
slowly dripping diethyl hypophosphorous acid into commercially available KH-560 under the protection of nitrogen, reacting the reaction system at a temperature of no more than 55 ℃ for 10-15 hours, adding a small amount of zinc oxide, stirring, filtering to remove insoluble substances, and removing a small amount of impurities under reduced pressure to obtain phosphorus-containing trialkoxysilane (KH-560P for short).
Further, in the S1, the reaction ratio of the phenyl trialkoxysilane to the phosphorus-containing trialkoxysilane is determined according to the phosphorus content, and the ratio of the phenyl trialkoxysilane to the phosphorus-containing trialkoxysilane is 50-5:1 in terms of molar ratio, and the preferable ratio is 25-10; the proportion of the phosphorus-containing trialkoxysilane is increased, and the melting point of the formed trapezoidal siloxane synergist is reduced.
Preferably, in the S2, the temperature of the organic phase mixture is increased to 70-85 ℃.
Preferably, in S2, adding potassium hydroxide-methanol solution as a catalyst, wherein the ratio of the mass of potassium hydroxide in the solution to that of phenyl trialkoxysilane in S1 is 0.2-1.0%, and performing reflux reaction to obtain a mixture with white precipitate; higher proportions of phenyltrialkoxysilane give a white product with a higher melting point.
The phosphorus-containing ladder-shaped polysiloxane prepared by the method is used as a flame-retardant synergist to be applied to flame-retardant nylon materials.
Furthermore, the flame-retardant synergist prepared by the invention can be combined with other polyamide auxiliaries to improve the processing property and mechanical property of the flame-retardant polyamide composition; wherein the polyamide auxiliary agent comprises one or more of flame retardant, filler, stabilizer, antioxidant, synergist and the like.
Preferably, the flame retardant is one or a combination of several of a phosphorus-nitrogen flame retardant, an organic phosphate flame retardant and an inorganic hypophosphite flame retardant; the organic phosphate flame retardant is preferably added in an amount of 8 to 20%, preferably 11 to 16%.
Preferably, the ratio of the flame retardant synergist to the flame retardant is 1.
Preferably, the flame retardant polyamide composition is used for plastics and fibers.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention introduces phenyl silicon units: the high-efficiency carbon formation is realized by introducing phenyl groups, the melting point of polysiloxane is improved, and the organosilicon modifier and the synergist are prevented from existing in a liquid state under common use conditions and being prevented from being separated out.
2. The glycerol phosphate ester unit is introduced, the flame retardant property is enhanced through the carbon forming effect of the phosphate ester at the high temperature stage, and particularly, the flame retardant effect is better in thinner products.
3. The invention belongs to phosphorus-silicon flame retardant, which can greatly reduce the use amount of the flame retardant and obviously improve the mechanical property of the product.
Drawings
FIG. 1 is a xrd spectrum of a phosphotapezium polysiloxane of the present invention;
FIG. 2 shows a process for preparing a ladder-type phosphorus-containing polysiloxane according to the present invention 31 P NMR spectrum.
FIG. 3 shows a thermogravimetric spectrum of a phosphotapetalate polysiloxane of the present invention.
Detailed Description
The invention is further explained below with reference to the figures and the specific embodiments;
examples
Raw materials: OP1230, clariant;
OP1312, clarien;
KH-560, commercially available;
diethylphosphinic acid, available from the company;
1. phosphorus-containing trialkoxysilane (KH-560P) is synthesized by the following method:
slowly dripping diethyl hypophosphorous acid into commercially available KH-560 under the protection of nitrogen, reacting at a temperature of no more than 55 ℃ for 10-15 hours, adding a small amount of zinc oxide, stirring, filtering to remove insoluble substances, and removing a small amount of impurities under reduced pressure to obtain phosphorus-containing trialkoxysilane (KH-560P for short).
2. Preparation method of phosphorus-containing ladder polysiloxane (560-PSQ):
a preparation method of phosphorus-containing ladder polysiloxane (560-PSQ) specifically comprises the following steps:
s1, taking 10kg of phenyltrimethoxysilane and 1kg of KH-560P, dissolving in 41.8L of toluene, cooling to a temperature of not more than 10 ℃, slowly dropwise adding 15L of 0.1mol/L hydrochloric acid, stirring at normal temperature for reaction for 12 hours, and adding pure water to wash the toluene layer until the washing liquid is neutral.
S2, filtering off a small amount of sticky substances, adding 3L of 0.02mol/L potassium hydroxide methanol solution, heating to 80 ℃, reacting for 24 hours, filtering off a part of white insoluble substances, washing an organic phase to be neutral, and removing the solvent to obtain white light powder, namely 560-PSQ for short.
And (4) testing results:
the X-ray powder diffraction pattern of the 560-PSQ sample was measured and, as shown, has a typical diffraction pattern of a typical ladder polysiloxane;
the 31P NMR spectrum of the 560-PSQ sample was tested and phosphorus was found to be present as an alkyl phosphate ester.
3. The processing method of the high polymer material comprises the following steps:
preparing OP1230+ phosphorus-containing trapezoidal polysiloxane (560-PSQ) and 30% glass fiber PA6 nylon according to a general processing method, blending, granulating and injection molding according to the following parts by weight, and testing the mechanical property and the flame retardant property of a processed product;
TABLE 1 compounding ratio and Performance test of comparative examples 1 to 3 and examples 1 to 4
The results show that: it can be seen that when only 13 parts of diethylphosphinate and 2 parts of ladder-shaped siloxane are used, the glass fiber reinforced nylon with the thickness of 0.8mm can reach UL-94V-0 grade, and the elongation at break and the non-notch impact are obviously superior to the OP1312 phosphorus-nitrogen flame-retardant scheme used in the current market.
Claims (9)
1. Preparation method of phosphorus-containing trapezoidal polysiloxane, and phosphorus-containing trapezoidal polysiloxane
The alkane has the following structural formula:
in the formula:
is a repeating group of a group represented by,
r is R 1 Or R 2 Wherein R is 1 Is phenyl, R 2 Is composed of
；
The method is characterized in that: the method specifically comprises the following steps:
s1, mixing and dissolving phenyl trialkoxysilane and phosphorus-containing trialkoxysilane in toluene, slowly adding hydrochloric acid, reacting at normal temperature for 5-15 hours, taking out and washing to be neutral, and drying an organic phase;
s2, heating the organic phase mixture to 60-90 ℃, adding a potassium hydroxide-methanol solution as a catalyst, performing reflux reaction to obtain a mixture with white precipitates, filtering insoluble substances, drying the filtrate, and evaporating the solvent to obtain a white solid product.
2. The method of preparing a polysiloxane comprising a phosphorus-containing ladder according to claim 1, wherein: in S1, the molar ratio of the phenyl trialkoxysilane to the phosphorus-containing trialkoxysilane is 50-5:1.
3. The method for producing the phosphorus-containing ladder polysiloxane according to claim 1 or 2, characterized in that: and (2) adding a potassium hydroxide-methanol solution as a catalyst, wherein the ratio of the mass of potassium hydroxide in the solution to the mass of the phenyltrialkoxysilane in the S1 is 0.2-1.0%.
4. Use of a phosphorus-containing ladder polysiloxane prepared according to the method of claim 3, wherein: the application of the flame retardant synergist in flame retardant nylon materials.
5. The use of the phosphorus-containing ladder polysiloxane of claim 4, wherein: the phosphorus-containing ladder-shaped polysiloxane and other polyamide auxiliaries are compounded and applied to the flame-retardant nylon material, wherein the polyamide auxiliaries comprise one or more of a flame retardant, a filler, a stabilizer, an antioxidant and a synergist.
6. The use of a phosphorus-containing ladder polysiloxane according to claim 5, wherein: the flame retardant is one or a combination of several of a phosphorus-nitrogen flame retardant, an organic phosphate flame retardant and an inorganic hypophosphite flame retardant.
7. The use of a phosphorus-containing ladder polysiloxane according to claim 6, wherein: the addition amount of the organic phosphate flame retardant is 8-20%.
8. Use of a phosphorus-containing ladder polysiloxane according to claim 5 or 7, wherein: the proportion of the flame-retardant synergist to the flame retardant is 1.
9. The use of a phosphorus-containing ladder polysiloxane according to claim 8, wherein: flame retardant polyamide compositions are used in plastics and fibers.
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Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08188649A (en) * | 1995-01-10 | 1996-07-23 | Kansai Shin Gijutsu Kenkyusho:Kk | Ladder polysiloxane and its production |
| CN1454919A (en) * | 2002-05-02 | 2003-11-12 | Dso国立实验室公司 | Ladder silicone polymer |
| TW200833731A (en) * | 2007-02-09 | 2008-08-16 | Chung Shan Inst Of Science | Manufacturing method of phophorous containing ladder polysilsesquioxane organic/inorganic nano composite material |
| CN101624445A (en) * | 2008-07-11 | 2010-01-13 | 北京化工大学 | Method for preparing trapezoidal phenyl polysiloxane |
| CN102167831A (en) * | 2011-03-12 | 2011-08-31 | 苏州大学 | Functional trapezoid polysilsequioxane and preparation method thereof |
| CN103145994A (en) * | 2013-04-01 | 2013-06-12 | 苏州大学 | Trapezoidal polysiloxane and preparation method thereof |
| CN106749414A (en) * | 2017-01-13 | 2017-05-31 | 山东船舶技术研究院 | A kind of phosphorous Silicone-containing Flame Retardant of response type and preparation method thereof |
| CN107057346A (en) * | 2017-01-20 | 2017-08-18 | 广东优科艾迪高分子材料有限公司 | Flame-retardant nylon composition |
| WO2017145690A1 (en) * | 2016-02-26 | 2017-08-31 | 国立大学法人 鹿児島大学 | Ladder-type polysilsesquioxane having phosphonic acid group and phosphonate group in side chains thereof, ladder-type polysilsesquioxane laminate, method for producing ladder-type polysilsesquioxane, and method for producing ladder-type polysilsesquioxane laminate |
| CN109021239A (en) * | 2018-08-30 | 2018-12-18 | 北京理工大学 | It is a kind of while there is phosphorous and double bond group Polyhedral oligomeric silsesquioxane and its preparation method and application |
| CN109134864A (en) * | 2018-08-30 | 2019-01-04 | 北京理工大学 | A kind of trapezoidal oligomeric silsesquioxane derivative and preparation method thereof |
| CN109233238A (en) * | 2018-08-30 | 2019-01-18 | 北京理工大学 | A kind of Polyhedral oligomeric silsesquioxane fire-retardant polycarbonate and its preparation method and application |
| CN109734914A (en) * | 2019-01-15 | 2019-05-10 | 苏州世华新材料科技股份有限公司 | A kind of phosphorus-contained organic silicon resin and preparation method thereof |
| CN109942819A (en) * | 2019-03-28 | 2019-06-28 | 北京理工大学 | A kind of preparation method of straight chain ladder-like poly-phenyl silsesquioxane |
| CN113402712A (en) * | 2021-06-24 | 2021-09-17 | 长兴特殊材料（珠海）有限公司 | Phosphorus-containing ladder-shaped polysiloxane and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7700711B2 (en) * | 2007-03-02 | 2010-04-20 | Chung Shan Institute Of Science And Technology, Armaments Bureau, M.N.D. | Manufacturing method of ladder-like phosphorous-containing polysilsesquioxanes nanocomposite material |
-
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Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08188649A (en) * | 1995-01-10 | 1996-07-23 | Kansai Shin Gijutsu Kenkyusho:Kk | Ladder polysiloxane and its production |
| CN1454919A (en) * | 2002-05-02 | 2003-11-12 | Dso国立实验室公司 | Ladder silicone polymer |
| TW200833731A (en) * | 2007-02-09 | 2008-08-16 | Chung Shan Inst Of Science | Manufacturing method of phophorous containing ladder polysilsesquioxane organic/inorganic nano composite material |
| CN101624445A (en) * | 2008-07-11 | 2010-01-13 | 北京化工大学 | Method for preparing trapezoidal phenyl polysiloxane |
| CN102167831A (en) * | 2011-03-12 | 2011-08-31 | 苏州大学 | Functional trapezoid polysilsequioxane and preparation method thereof |
| CN103145994A (en) * | 2013-04-01 | 2013-06-12 | 苏州大学 | Trapezoidal polysiloxane and preparation method thereof |
| WO2017145690A1 (en) * | 2016-02-26 | 2017-08-31 | 国立大学法人 鹿児島大学 | Ladder-type polysilsesquioxane having phosphonic acid group and phosphonate group in side chains thereof, ladder-type polysilsesquioxane laminate, method for producing ladder-type polysilsesquioxane, and method for producing ladder-type polysilsesquioxane laminate |
| CN106749414A (en) * | 2017-01-13 | 2017-05-31 | 山东船舶技术研究院 | A kind of phosphorous Silicone-containing Flame Retardant of response type and preparation method thereof |
| CN107057346A (en) * | 2017-01-20 | 2017-08-18 | 广东优科艾迪高分子材料有限公司 | Flame-retardant nylon composition |
| CN109021239A (en) * | 2018-08-30 | 2018-12-18 | 北京理工大学 | It is a kind of while there is phosphorous and double bond group Polyhedral oligomeric silsesquioxane and its preparation method and application |
| CN109134864A (en) * | 2018-08-30 | 2019-01-04 | 北京理工大学 | A kind of trapezoidal oligomeric silsesquioxane derivative and preparation method thereof |
| CN109233238A (en) * | 2018-08-30 | 2019-01-18 | 北京理工大学 | A kind of Polyhedral oligomeric silsesquioxane fire-retardant polycarbonate and its preparation method and application |
| CN109734914A (en) * | 2019-01-15 | 2019-05-10 | 苏州世华新材料科技股份有限公司 | A kind of phosphorus-contained organic silicon resin and preparation method thereof |
| CN109942819A (en) * | 2019-03-28 | 2019-06-28 | 北京理工大学 | A kind of preparation method of straight chain ladder-like poly-phenyl silsesquioxane |
| CN113402712A (en) * | 2021-06-24 | 2021-09-17 | 长兴特殊材料（珠海）有限公司 | Phosphorus-containing ladder-shaped polysiloxane and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| "逐步偶联聚合反应"在研制有序交联高分子及复合物中的应用;谢萍等;《高分子通报》;19971230(第04期);第203-211、231页 * |
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