阅读说明：本技术 一种含磷的反应型阻燃剂、硅橡胶组合物、制备方法及应用 (Phosphorus-containing reactive flame retardant, silicone rubber composition, preparation method and application ) 是由 潘庆崇 于 2019-08-28 设计创作，主要内容包括：本发明提供了一种含磷的反应型阻燃剂、硅橡胶组合物、制备方法及应用,所述含磷的反应型阻燃剂由带有-P-H反应基团的化合物与不饱和醇类化合物通过加成反应得到；本发明提供的含磷的反应型阻燃剂,具有活性的基团羟基,可以参与到制备复合材料的反应中,通过反应使得含磷的反应型阻燃剂与复合材料的结合更加稳定,使得最终得到的材料物理性能优良,拉伸强度、断裂伸长率均大幅提升,自身的燃烧性以及浸水后的燃烧性均达到了UL-94V-0级,并且避免了添加型阻燃剂易溶于水而析出的现象,应用前景良好。(The invention provides a phosphorus-containing reactive flame retardant, a silicon rubber composition, a preparation method and application, wherein the phosphorus-containing reactive flame retardant is obtained by an addition reaction of a compound with a-P-H reactive group and an unsaturated alcohol compound; the phosphorus-containing reactive flame retardant provided by the invention has active hydroxyl groups, can participate in the reaction for preparing the composite material, and the phosphorus-containing reactive flame retardant and the composite material are combined more stably through the reaction, so that the finally obtained material has excellent physical properties, the tensile strength and the elongation at break are greatly improved, the self combustibility and the combustibility after soaking reach the UL-94V-0 level, the phenomenon that an additive flame retardant is easily dissolved in water and separated out is avoided, and the application prospect is good.)

1. The phosphorus-containing reactive flame retardant is characterized by being obtained by an addition reaction of a compound with a-P-H reactive group and an unsaturated alcohol compound.

2. The reactive phosphorus-containing flame retardant of claim 1, wherein the compound having a reactive group-P-H has a structure according to formula I:

wherein X is a VI main group element or is absent, L₁、L₂Each independently is preferably alkyl, cycloalkyl, aryl, heteroaryl, alkoxy, alkanoyl or aryloxy, or L₁And L₂Are connected into a ring.

3. The reactive phosphorus-containing flame retardant according to claim 2, wherein X is preferably an oxygen atom or a sulfur atom, and further preferably an oxygen atom;

preferably, said L₁、L₂Are each independently preferably C₁-C₅Alkoxy group of (C)₆-C₉Aryl or C of₆-C₉Aryloxy group of, or L₁And L₂Are connected into a ring.

4. The reactive phosphorus-containing flame retardant according to any one of claims 1 to 3, wherein the unsaturated alcohol compound comprises an enol compound, an alkynol compound, or an alcohol compound containing an epoxy group;

preferably, the unsaturated alcohol compound is preferably an enol compound;

preferably, the structure of the enol compound is preferablyR₁、R₂Are independently selected from any one of hydrogen, hydroxyl substituted alkyl or hydroxyl substituted aryl and R₁、R₂Not hydrogen at the same time; r₃Is C₁～C₆And at least one hydroxyl group.

5. The reactive phosphorus-containing flame retardant of claim 4, wherein R is₁、R₂Is a hydroxy-substituted alkyl group;

preferably, said R is₃Is substituted by at least one hydroxy group C₃～C₄Alkyl group of (1).

6. The reactive flame retardant containing phosphorus according to any one of claims 1 to 5, wherein the reactive flame retardant containing phosphorus is preferably one containing phosphorus Any one of them.

7. The reactive flame retardant containing phosphorus according to claim 6, wherein the reactive flame retardant containing phosphorus is preferably one containing phosphorus Any one of them.

8. The method of any of claims 1-7, wherein the method comprises: and carrying out addition reaction on a compound with a-P-H reaction group and an unsaturated alcohol compound to obtain the phosphorus-containing reactive flame retardant.

9. The silicone rubber composition is characterized by comprising the following components in parts by weight: the reactive flame retardant according to any one of claims 1 to 7, which comprises 60 to 90 parts by weight of phenyltrimethoxysilane, 50 to 70 parts by weight of phenyltrimethoxysilane, 40 to 70 parts by weight of vinyltrimethoxysilane, and 5 to 20 parts by weight of benzenesulfonic acid.

10. Use of the silicone rubber composition according to claim 9 in medical devices or automotive parts.

Technical Field

The invention belongs to the field of flame retardants, and relates to a phosphorus-containing reactive flame retardant, a silicone rubber composition, a preparation method and an application.

Background

With the enhancement of people's fire protection consciousness and the development of socioeconomic, the development of various low-toxicity and high-efficiency flame retardants has become a great trend. The currently used flame retardants mainly comprise three major classes of organic halogen series, organic phosphorus series and inorganic series, and the phosphorus series flame retardants are the most potential flame retardants in the modern generation.

The reactive flame retardant has the characteristics of lasting flame retardant effect, no migration in epoxy resin, improvement of flame retardant capability of the epoxy resin, maintenance or improvement of mechanical properties of the epoxy resin and the like. Therefore, the development of the phosphorus-based reactive flame retardant has higher value for application.

CN102167791A discloses a reactive flame retardant for flexible polyurethane foam and application thereof, belonging to the technical field of flame retardants. The reactive flame retardant contains three components: a phosphorus-containing polyol, a halogen-containing polyol and a 2-functional chain extender. When in use, the reactive flame retardant can be directly added into polyether polyol, has good compatibility with the polyether polyol and cannot be separated out. The flame retardant has the characteristics of lasting flame retardant effect, low VOC and low atomization, the flame retardant effect after aging cannot be reduced, and the physical properties of the foam are not negatively affected. The soft foam using the flame retardant has excellent flame recombination performance and high peeling strength, and is suitable for interior materials of automobiles and airplanes. The method mainly improves the indentation hardness, and other physical strength is improved a little.

CN105175777A discloses a phosphorus-nitrogen synergistic reaction type flame retardant for polyurethane, a preparation method and an application thereof, in the method, epoxy chloropropane and an alcohol amine compound are subjected to ring opening and ring closing reaction in an organic solvent according to a reaction molar ratio, and then the reaction intermediate glycidol amine which is viscous and liquid at room temperature is obtained after filtration and decompression for removing the solvent. And then the reaction of DOPO and epoxy group is utilized to form the reactive flame retardant with the end group of dihydroxy and the DOPO flame retardant group. The flame retardant has a phosphorus-nitrogen synergistic flame retardant effect, is environment-friendly, non-toxic and low-smoke, can be used as a chain extender to be applied to preparation of structural flame retardant polyurethane materials, and is simple in preparation process and remarkable in flame retardant effect. The polyurethane material synthesized by the flame retardant has good mechanical properties, the oxygen index is improved to 27-29%, and the flame retardant grade can reach UL-94V-0 grade. The flame retardant provided by the method can play a role only by using the synergy of phosphorus and nitrogen, and has certain limitation.

At present, the physical properties and the flame retardant properties of the phosphorus-containing reactive flame retardant are yet to be further enhanced, and the development of a novel phosphorus-containing reactive flame retardant has important value for further expanding the application range.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a phosphorus-containing reactive flame retardant, a silicon rubber composition, a preparation method and application so as to achieve the effects of improving the physical properties and flame retardance of the phosphorus-containing reactive flame retardant.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the invention provides a phosphorus-containing reactive flame retardant, which is obtained by an addition reaction of a compound with a-P-H reactive group and an unsaturated alcohol compound.

The phosphorus-containing reactive flame retardant provided by the invention has active hydroxyl groups, can participate in the reaction for preparing the composite material, and the phosphorus-containing reactive flame retardant and the composite material are combined more stably through the reaction, so that the finally obtained material has excellent physical properties, the tensile strength and the elongation at break are greatly improved, the self combustibility and the combustibility after soaking reach the UL-94V-0 level, the phenomenon that an additive flame retardant is easily dissolved in water and separated out is avoided, and the application prospect is good.

Preferably, the compound having a-P-H reactive group has the structure shown in formula I:

wherein X is a VI main group element or is absent, L₁、L₂Each independently is preferably alkyl, cycloalkyl, aryl, heteroaryl, alkoxy, alkanoyl or aryloxy, or L₁And L₂Are connected into a ring.

Preferably, X is an oxygen atom or a sulfur atom, and further preferably an oxygen atom.

Preferably, said L₁、L₂Are each independently preferably C₁-C₅Alkoxy group of (C)₆-C₉Aryl or C of₆-C₉Aryloxy group of, or L₁And L₂Are connected into a ring.

Wherein, C₁-C₅May be C₁、C₂、C₃、C₄Or C₅Etc. C₆-C₉May be C₆、C₇、C₈Or C₉₃And the like.

Illustratively, the compound having a-P-H reactive group may be 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), dimethyl phosphite, diethyl phosphite or diphenyl phosphite, and the like.

Preferably, the unsaturated alcohol compound includes an enol compound, an alkynol compound or an alcohol compound containing an epoxy group.

Preferably, the unsaturated alcohol compound is an enol compound.

Preferably, the enol compound has a structure ofR₁、R₂Are independently selected from any one of hydrogen, hydroxyl substituted alkyl or hydroxyl substituted aryl and R₁、R₂Not hydrogen at the same time; r₃Is C₁～C₆And at least one hydroxyl group.

Illustratively, R₃Is C₁When it is in the structure ofR₃Is C₂When it is in the structure of Or may be substituted by two hydroxy groupsNamely R₃At least one of the carbon atoms forming a ring and substituted by at least one hydroxyl group。

Preferably, said R is₁、R₂Is a hydroxyl-substituted alkyl group.

Preferably, said R is₃Is substituted by at least one hydroxy group C₃～C₄Alkyl group of (1).

Preferably, the phosphorus-containing reactive flame retardant is preferably Any one of them.

Preferably, the phosphorus-containing reactive flame retardant is preferably Any one of them.

In the invention, the performances of the compounds with different structures do not follow a certain rule, and comprehensive research finds that the physical properties and the flame retardant effect of the compound with the 3 structures are the best.

In a second aspect, the present invention provides a method for preparing the phosphorus-containing reactive flame retardant according to the first aspect, the method comprising: and carrying out addition reaction on a compound with a-P-H reaction group and an unsaturated alcohol compound to obtain the phosphorus-containing reactive flame retardant.

In a third aspect, the invention provides a silicone rubber composition, which comprises the following components in parts by weight: 60 to 90 parts (for example, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, or 90 parts) of the phosphorus-containing reactive flame retardant of the first aspect, 50 to 70 parts (for example, 50 parts, 55 parts, 60 parts, 65 parts, or 70 parts) of phenyltrimethoxysilane, 40 to 70 parts (for example, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, or 70 parts) of vinyltrimethoxysilane, and 5 to 20 parts (for example, 5 parts, 10 parts, 15 parts, or 20 parts) of benzenesulfonic acid.

In a fourth aspect, the present invention provides a use of the silicone rubber composition according to the third aspect in medical devices or automobile parts.

In medical appliances, silicone rubber anti-noise earplugs, silicone rubber artificial blood vessels, silicone rubber tympanic membrane repair patches and the like can be made; in automobile parts, various key parts can be prepared.

Compared with the prior art, the invention has the following beneficial effects:

the phosphorus-containing reactive flame retardant provided by the invention has active hydroxyl groups, can participate in the reaction for preparing the composite material, and the phosphorus-containing reactive flame retardant and the composite material are combined more stably through the reaction, so that the finally obtained material has excellent physical properties, the tensile strength and the elongation at break are greatly improved, the self combustibility and the combustibility after soaking reach the UL-94V-0 level, the phenomenon that an additive flame retardant is easily dissolved in water and separated out is avoided, and the application prospect is good.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

Example 1

The embodiment provides a phosphorus-containing reactive flame retardant, which has the following structure:

the preparation method comprises the following steps: 1mol of dimethyl phosphite and 1mol of propylene alcohol are added into a high-pressure kettle and heated to 200 ℃ for reaction for 5 hours to obtain the phosphorus-containing reactive flame retardant.

¹H NMR(400MHz,DMSO-d₆)δ4.87(t,J＝5.5Hz,1H),3.66(d,J＝10.8Hz,6H),3.25(ddd,J＝12.5,7.0,5.6Hz,1H),3.04(ddd,J＝12.6,7.0,5.6Hz,1H),1.69(dq,J＝11.5,6.8Hz,1H),1.09(d,J＝6.7Hz,3H).

Example 2

The embodiment provides a phosphorus-containing reactive flame retardant, which has the following structure:

the preparation method comprises the following steps: 1mol of dimethyl phosphite and 1mol of 2-butenol are added into a high-pressure autoclave and heated to 250 ℃ for reaction for 4 hours to obtain the phosphorus-containing reactive flame retardant.

¹H NMR(400MHz,DMSO-d₆)δ4.48(t,J＝5.6Hz,1H),3.66(d,J＝10.8Hz,6H),3.47(dddd,J＝12.4,7.0,5.4,1.2Hz,1H),3.20(ddd,J＝12.3,6.9,5.6Hz,1H),1.75–1.44(m,3H),0.82(t,J＝7.9Hz,3H).

Example 3

The embodiment provides a phosphorus-containing reactive flame retardant, which has the following structure:

the preparation method comprises the following steps: 1mol of diethyl phosphite and 1mol of 1, 4-butylene glycol are added into a high-pressure autoclave and heated to 230 ℃ for reaction for 4 hours to obtain the phosphorus-containing reaction type flame retardant.

¹H NMR(400MHz,DMSO-d₆)δ7.33(t,J＝5.5Hz,1H),4.23(t,J＝5.5Hz,1H),4.06(dp,J＝12.3,8.1Hz,2H),3.67(dp,J＝12.3,8.1Hz,2H),3.53–3.17(m,4H),2.18(tt,J＝12.6,7.1Hz,1H),1.72(dddd,J＝13.8,7.8,6.6,1.3Hz,1H),1.36(t,J＝8.0Hz,6H),1.21(m,1H).

Example 4

The embodiment provides a phosphorus-containing reactive flame retardant, which has the following structure:

the preparation method comprises the following steps: 1mol of DOPO and 1mol of 3-butene-1-ol are added into a high-pressure autoclave and heated to 230 ℃ for reaction for 4 hours to obtain the phosphorus-containing reactive flame retardant.

¹H NMR(400MHz,DMSO-d₆)δ8.03–7.28(m,8H),4.15(t,J＝5.5Hz,1H),3.32(m,1H),3.07(m,1H),2.00–1.68(m,2H),1.47–1.17(m,4H).

Example 5

The embodiment provides a phosphorus-containing reactive flame retardant, which has the following structure:

the preparation method comprises the following steps: 1mol of diphenyl phosphite and 1mol of allyl alcohol are added into an autoclave and heated to 200 ℃ for reaction for 4 hours to obtain the phosphorus-containing reactive flame retardant.

¹H NMR(400MHz,DMSO-d₆)δ7.45–7.11(m,10H),4.46(t,J＝5.5Hz,1H),3.33(ddd,J＝12.4,7.0,5.5Hz,1H),3.08(ddd,J＝12.5,7.0,5.5Hz,1H),1.67(dp,J＝11.5,6.9Hz,1H),1.16(d,J＝6.7Hz,3H).

Example 6

The embodiment provides a phosphorus-containing reactive flame retardant, which has the following structure:

the preparation method comprises the following steps: 1mol of diethyl phosphite and 1mol of 2-cyclohexenol are added into a high-pressure autoclave and heated to 250 ℃ for reaction for 4 hours to obtain the phosphorus-containing reactive flame retardant.

¹H NMR(400MHz,DMSO-d₆)δ3.90(dp,J＝12.3,8.1Hz,2H),3.69(dp,J＝12.5,8.1Hz,2H),3.51(m,1H),2.99(d,J＝5.0Hz,1H),2.19(m,1H),2.01–1.06(m,14H).

The phosphorus-containing reactive flame retardants provided in examples 1-6 were prepared as silicone rubber compositions

The preparation method comprises the following steps: mixing the components at 60 ℃ for 8h, and adding a proper amount of catalyst (generally 10 parts) to obtain the silicone rubber, wherein the components are prepared according to the following formula 1:

TABLE 1

The units of data in the tables are all "parts". The phosphorus-containing reactive flame retardants of examples 1 to 6 correspond to silicone rubber compositions 1 to 6, respectively.

And (3) performance testing:

the silicone rubber compositions 1-7 were subjected to performance testing as follows:

(1) combustibility: testing according to UL-94 vertical burning test standard;

(2) tensile strength and elongation: according to the regulation of GB/T528-2009;

(3) flame retardant stability: after soaking the polyester composition in water for 1h, it was dried and its flammability was measured again.

The results of the tests are shown in table 2:

TABLE 2

As can be seen from the data in Table 2, the phosphorus-containing reactive flame retardant provided by the invention has better flame retardant property, excellent physical property and good stability, and the flame retardant property is not affected after water washing. The comparison of the silicone rubber compositions 1-6 shows that the silicone rubber compositions 3, 4, 5 have relatively better overall properties, wherein the tensile strength is above 3.7MPa and the elongation at break is above 108%, which indicates that the phosphorus-containing reactive flame retardant with the structure has better performance when applied.

The applicant states that the present invention is illustrated by the above examples to the phosphorus-containing reactive flame retardant, silicone rubber composition, preparation method and application of the present invention, but the present invention is not limited to the above detailed method, i.e. it does not mean that the present invention must be implemented by relying on the above detailed method. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.