Flame-retardant polyurethane composite material with low candlewick effect and preparation method thereof
By aminating and flame retardant modification of glass fibers, combined with optimized resin composition and preparation process, the problem of difficult to take into account both the flame retardant properties and mechanical properties caused by the "candle wick effect" in polyurethane composite materials, achieving low " The preparation of flame-retardant polyurethane composite materials with wick effect improves production efficiency and flame retardant performance.
Patent Information
- Application Number
- CN202411372701.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-29
- Publication Date
- 2025-02-11
AI Technical Summary
Polyurethane composites have a "wick effect" in applications, which makes it difficult to take into account both flame retardant performance, production efficiency and mechanical properties.
By aminating and flame retardant modification of glass fibers, a flame retardant polyurethane composite with low "wick effect" was prepared using DOPO-PH flame retardant, combined with optimized resin composition and preparation process.
It effectively suppresses the "candle wick effect", reduces the amount of flame retardant, maintains the mechanical properties of the composite material, improves production efficiency, and achieves the consideration of flame retardant performance, mechanical properties and production efficiency.
Smart Images
Figure CN119410127A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of flame retardant modification of composite materials, and in particular to a flame retardant polyurethane composite material with low candle wick effect and a preparation method thereof. Background Art
[0002] Polyurethane (PU), as a high-performance polymer material, is widely used in furniture, automobiles, construction, footwear, coatings, adhesives, sealants, foam products and other fields due to its excellent mechanical properties, chemical resistance, flexibility and wear resistance. The performance characteristics of polyurethane materials are mainly as follows: 1. Excellent mechanical properties: polyurethane materials have high strength and elastic modulus, and can withstand large stress without deformation or fracture. 2. Good wear resistance: polyurethane has excellent wear resistance and is suitable for making parts that require frequent contact and friction. 3. Flexibility: polyurethane can adjust its hardness and flexibility according to different formulas, and is suitable for making soft and hard materials. 4. Chemical resistance: polyurethane has good resistance to a variety of chemicals and is not easily corroded. 5. Adhesion: polyurethane can be used as a high-performance adhesive with excellent adhesion. 6. Thermal insulation: polyurethane foam has excellent thermal insulation and is widely used in building insulation materials. 7. Processability: Polyurethane materials are easy to process and can be used to manufacture products with complex shapes through various processes such as casting, spraying, and extrusion.
[0003] However, in practical applications, polyurethane materials also face some challenges. Especially in composite materials, if the distribution of fibers or particles is uneven, or there are differences in the physical properties of the material such as the thermal expansion coefficient and thermal conductivity coefficient, the internal temperature field and heat flow field will show uneven distribution. This unevenness will form a "candle wick"-shaped channel along the axis of the fiber or particle during the heat transfer from the high temperature area to the low temperature area, which is called the "candle wick effect". The "candle wick effect" will accelerate the heat transfer speed, causing the local temperature of the material to rise, increasing the fire hazard of the material. In order to meet the flame retardant requirements of polyurethane materials, the current common solution is to add flame retardants to the resin during molding. However, due to the existence of the "candle wick effect", in order to achieve the flame retardancy of the composite material, the amount of flame retardant added must be increased. This not only increases the cost of the material, but also has a significant impact on the mechanical properties, life and production efficiency of the composite material. Summary of the invention
[0004] The present invention aims to provide a flame retardant polyurethane composite material with low candle wick effect and a preparation method thereof, so as to solve the problem that the flame retardancy and mechanical properties of the polyurethane composite material in the prior art cannot be taken into account at the same time.
[0005] To achieve the above-mentioned purpose, the present invention adopts the following technical scheme: a flame-retardant polyurethane composite material with low candle wick effect, comprising a resin component and a flame-retardant modified glass fiber, the resin component being composed of the following raw materials in parts by weight: 51 to 54 parts of isocyanate, 40 to 44 parts of polyol, 2 parts of release agent, and 0 to 7 parts of flame retardant; the flame-retardant modified glass fiber is obtained by amino-modifying and flame-retardantly modifying glass fiber.
[0006] Preferably, as an improvement, the isocyanate is at least one of toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HDI), lysine diisocyanate (LDI), and naphthalene diisocyanate (NDI).
[0007] Preferably, as an improvement, the polyol is at least one of polyether polyol, polyester polyol, polyacrylate, and bio-based polyol.
[0008] Preferably, as an improvement, the release agent is at least one of a hydroxy acid-modified polysiloxane internal release agent, an amine-modified polysiloxane internal release agent, a polyether-modified polysiloxane internal release agent, an organosilicon release agent, and an emulsified oil.
[0009] Preferably, as an improvement, the flame retardant is at least one of a phosphorus-based flame retardant (dimethyl methylphosphonate, diethyl ethyl phosphate, trichloroethyl phosphate, tris(2-chloropropyl) phosphate), a bromine-based flame retardant (hexabromocyclododecane, hexabromobiphenyl), a nitrogen-based flame retardant (melamine, dicyandiamide, guanidine salt), and an inorganic flame retardant (zinc borate, aluminum hydroxide hydrate, barium metaborate).
[0010] Preferably, as an improvement, when the glass fiber is amino-modified, the coupling agent used is an amino coupling agent, and the amino coupling agent is at least one of 3-aminopropyltriethoxysilane (KH550), 3-aminopropyltrimethoxysilane (APS), N(2-aminoethyl)3-aminopropylmethoxysilane (AAPS), and N(2-aminoethyl)3-propylaminomethoxymethylsilane (AEAPS), and the amount of the amino coupling agent added is 1wt%.
[0011] Preferably, as an improvement, when the glass fiber is flame-retardant modified, the flame retardant used is DOPO-PH, and the added amount of DOPO-PH is DOPO-PH / aminated modified glass fiber = 1%-10%.
[0012] Preferably, as an improvement, the structural formula of DOPO-PH is as follows (1):
[0013]
[0014] Preferably, as an improvement, the preparation method of DOPO-PH comprises the following steps:
[0015] S1, mixing 4-aminophenol, 4-hydroxybenzaldehyde and methanol, and stirring to obtain system I;
[0016] S2, adding methanol to system I and cooling in an ice-water bath to precipitate the product 2-[(phenylimino)methyl]phenol, filtering and separating the solid and washing with cold methanol;
[0017] S3, dissolving 2-[(phenylimino)methyl]phenol and DOPO in THF, heating and stirring the mixture to obtain System II;
[0018] S4. The white precipitate in system II was filtered and washed with cold THF, and then dried under vacuum to obtain white powder DOPO-PH.
[0019] Preferably, as an improvement, a method for preparing a flame-retardant polyurethane composite material with low wick effect comprises the following steps:
[0020] Step 1: treating the glass fiber: performing amino modification and flame retardant modification on the glass fiber to obtain flame retardant modified glass fiber;
[0021] Step 2, glue injection: inject the resin into the mold through a glue injection machine and mix it with the flame retardant modified glass fiber. The two are mixed in a mass ratio of 7.5-8:2-2.5. The resin component is composed of the following raw materials in mass parts: 51-54 parts of isocyanate, 40-44 parts of polyol, 2 parts of release agent, and 0-7 parts of flame retardant;
[0022] Step 3: Molding: Curing and molding using a molding mold to obtain a flame-retardant polyurethane composite material with low "wick effect".
[0023] The principle and advantage of this solution are: in actual application, in this technical solution, in view of the "wick effect" existing in the prior art when glass fiber is used in composite materials, which leads to the problem that the flame retardant performance, production efficiency and mechanical properties of the composite materials cannot be taken into account, the present invention modifies the surface of the glass fiber, performs amino modification on the glass fiber, and then performs flame retardant modification. In the flame retardant modification stage of the glass fiber, this technical solution applies the DOPO-PH flame retardant to the modification of the glass fiber for the first time. DOPO-PH can self-crosslink to form carbon at a relatively low temperature and pyrolyze small molecules with polymer materials at high temperature to crosslink to generate a carbon layer with high thermal stability, so that the glass fiber material modified by this technical solution has a good "wick effect" suppression effect, and can further reduce the amount of flame retardant used in the material and maintain the mechanical properties of the composite material, improve the production efficiency of the flame retardant composite material, and achieve a balance of the three, which has outstanding economic effects and important significance in the industry.
[0024] Moreover, when the flame-retardant modified glass fiber is applied to the preparation of polyurethane composite materials, the technical scheme comprehensively and systematically optimizes the formula and preparation process of the flame-retardant modified polyurethane composite materials. Firstly, the flame-retardant modified glass fiber is used in the composition of the raw materials, which can reduce the amount of flame retardant added to the resin and reduce the influence of the flame retardant on the resin reaction molding. Moreover, through the amino modification and flame-retardant modification of the glass fiber, its compatibility with the resin material in the subsequent compounding can be guaranteed. In the optimization of the preparation process, the pultrusion speed of the flame-retardant composite material is improved, and the production efficiency is improved. BRIEF DESCRIPTION OF THE DRAWINGS
[0025] Figure 1 This is a physical picture of the composite pultrusion product of Example 1 of the present invention.
[0026] Figure 2 This is a physical picture of the composite pultrusion product of Comparative Example 1 of the present invention.
[0027] Figure 3 It is a flow chart of the flame retardant polyurethane processing system with base salary main effect in an embodiment of the present invention. DETAILED DESCRIPTION
[0028] The following is further described in detail through specific implementations, but the implementation of the present invention is not limited thereto. Unless otherwise specified, the technical means used in the following implementations are conventional means well known to those skilled in the art; the experimental methods used are all conventional methods; the materials, reagents, etc. used can all be obtained from commercial channels.
[0029] The figure marks in the drawings of the specification include: yarn frame 1, yarn ball 2, first tensioning wheel 3, first yarn dividing plate 4, amino modification pool 5, second yarn dividing plate 6, first reflux tank 7, first oven 8, second tensioning wheel 9, third yarn dividing plate 10, DOPO-PH pool 11, fourth yarn dividing plate 12, second reflux tank 13, second oven 14, third tensioning wheel 15, polyurethane pool 16, dipping rod 17, fifth yarn dividing plate 18, third reflux tank 19, molding mold 20, mold heating device 21, first traction device 22, second traction device 23, cutting machine 24.
[0030] Program Overview:
[0031] A flame-retardant polyurethane composite material with low candle wick effect comprises, by weight, 7.5-8 parts of flame-retardant modified glass fiber and 2-2.5 parts of a resin component; the flame-retardant modified glass fiber is obtained by sequentially subjecting the glass fiber to amino modification and flame-retardant modification; the resin component consists of the following raw materials in weight: 51-54 parts of isocyanate, 40-44 parts of polyol, 2 parts of a release agent and 0-7 parts of a flame retardant.
[0032] The isocyanate is at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate and naphthalene diisocyanate.
[0033] The polyol is at least one of polyether polyol, polyester polyol, polyacrylate, and bio-based polyol.
[0034] The release agent is at least one of hydroxy acid-modified polysiloxane internal release agent, amine-modified polysiloxane internal release agent, polyether-modified polysiloxane internal release agent, silicone release agent, and emulsified oil.
[0035] The flame retardant is at least one of phosphorus-based flame retardants (dimethyl methylphosphonate, diethyl ethyl phosphate, trichloroethyl phosphate, tris(2-chloropropyl) phosphate), bromine-based flame retardants (hexabromocyclododecane, hexabromobiphenyl), nitrogen-based flame retardants (melamine, dicyandiamide, guanidine salts), and inorganic flame retardants (zinc borate, aluminum hydroxide hydrate, barium metaborate).
[0036] A method for preparing a flame-retardant polyurethane composite material with low candle wick effect comprises the following steps:
[0037] Step 1: Processing of glass fiber:
[0038] S1. Amino modification of glass fiber: 100 g of GF (glass fiber) was dispersed in ethanol / water (500 ml, the mass ratio of ethanol to water was 450:50), and 1 wt% of an amino coupling agent (at least one of 3-aminopropyltriethoxysilane (KH550), 3-aminopropyltrimethoxysilane (APS), N(2-aminoethyl)3-aminopropylmethoxysilane (AAPS), and N(2-aminoethyl)3-propylaminomethoxymethylsilane (AEAPS)) was added under high-speed stirring, and the reaction was carried out from room temperature to 60-100° C. for 1-2 min. After the reaction was completed, the mixture was filtered, washed, and dried at 80° C. to obtain the amino glass fiber GF-NH 2， Its structural formula is as shown in formula (I).
[0039]
[0040] S2. Preparation of DOPO-PH: 4-aminophenol (10.9 g, 0.1 mole), 4-hydroxybenzaldehyde (12.2 g, 0.1 mole) and methanol were placed in a three-necked round-bottom flask equipped with a magnetic stirrer. The resulting mixture was stirred at 50°C for 5 h under a nitrogen atmosphere. The product 2-[(phenylimino)methyl]phenol was precipitated by adding methanol (200 ml) and cooling the resulting solution with an ice-water bath, and then the solid was separated by filtration and washed with cold methanol. Then, 2-[(phenylimino)methyl]phenol (10 g, 0.05 mole) and DOPO (21.6 g, 0.1 mole) were dissolved in THF (100 ml) at room temperature under a nitrogen atmosphere. The mixture was heated to 60°C and stirred for 12 h. The resulting white precipitate was filtered and washed several times with cold THF, and then dried under vacuum. The white powder was marked as DOPO-PH, and the structural formula of DOPO-PH is as shown in Formula (II).
[0041]
[0042]
[0043] S3. Synthesis of GF@DOPO-PH: GF-NH2 (100 g) was evenly dispersed in ethanol (500 ml, the mass ratio of ethanol to water was 450:50), and the DOPO-PH prepared in step 2 was dissolved in 100 ml of ethanol and slowly dripped into the above solution, wherein DOPO-PH / GF-NH2 = 1%-10%. After the addition was completed, the reaction was continued for 1-10 minutes. After the reaction was completed, it was filtered, washed, and dried at 80°C to obtain the flame retardant modified glass fiber GF@DOPO-PH, with a structural formula as shown in formula (III).
[0044]
[0045] Step 2: inject the resin into the mold through a glue injection machine and mix it with the flame retardant modified glass fiber in a mass ratio of 7.5-8:2-2.5;
[0046] The resin material includes 51 to 54 parts of isocyanate, 40 to 44 parts of polyol, 2 parts of release agent, and 0 to 7 parts of flame retardant.
[0047] Step three, molding, curing and molding the mixed system of step two with a molding mold, the molding conditions are injection pressure 1±0.2Mpa, mold temperature 160±10℃, 170±10℃, 180±10℃, and pultrusion speed 0.4-0.7m / min.
[0048] In this embodiment, the flame-retardant polyurethane composite material with low wick effect is manufactured by using a flame-retardant polyurethane composite material processing system, which includes a glass fiber amination modification unit, a DOPO-PH processing unit, a pultrusion unit and a cutting unit.
[0049] The glass fiber amination modification unit is used for amination modification of glass fiber, and includes a first tension wheel 3, a first yarn separation plate 4, an amination modification pool 5, a second yarn separation plate 6, a first reflux tank 7 and a first oven 8 arranged in sequence, and an amination modification solution (amino coupling agent KH550) is contained in the amination modification pool 5. A yarn rack 1 is fixed to the feed end of the amination modification unit, and a plurality of yarn balls 2 are placed on the yarn rack 1, so that multiple yarn balls 2 can be processed simultaneously, and the system operation efficiency can be ensured.
[0050] The DOPO-PH treatment unit comprises a second tension wheel 9, a third yarn separation plate 10, a DOPO-PH tank 11, a fourth yarn separation plate 12, a second reflux tank 13 and a second oven 14 which are arranged in sequence. The DOPO-PH tank 11 contains a DOPO-PH mixed solution.
[0051] The pultrusion unit includes a third tension wheel 15, a polyurethane pool 16, a dipping rod 17, a fifth yarn dividing plate 18, a third reflow groove 19 and a forming mold 20, which are arranged in sequence. A first traction device 22 is arranged at the discharge end of the forming mold 20, and a mold heating device 21 for heating the forming mold 20 is arranged between the first traction device 22 and the forming mold 20. A second traction device 23 is arranged on the right side of the first traction device 22, and a cutting unit is arranged on the right side of the second traction device 23. A plurality of dipping rods 17 are arranged, and the plurality of dipping rods 17 are arranged in the polyurethane pool 16 for full contact between the glass fiber and the polyurethane.
[0052] The cutting unit is a cutter 24 .
[0053] When the flame retardant polyurethane composite material is processed by the above processing system, first, the amination modification solution and the DOPO-PH mixed solution are respectively fed into the amination modification pool 5 and the DOPO-PH pool 11. Then, the glass fibers fixed on the creel 1 pass through the first tensioning wheel 3 and the first yarn dividing plate 4 and are immersed in the amination modification solution for amination modification, and then dried in the first oven 8.
[0054] The dried glass fiber is further pulled, flame-retardant modified by the DOPO-PH mixed solution and further dried by the second oven 14. The flame-retardant modified glass fiber is mixed with the resin material in the polyurethane pool 16 to form a mixed system, which enters the molding die 20 and is heated and cured by the die heating device 21 to obtain a low "wick effect" flame-retardant composite material profile. The low "wick effect" flame-retardant composite material profile enters the cutting unit under the traction of the first and second traction devices 23 and is cut to a fixed length by the cutting machine 24.
[0055] Example 1
[0056] A flame-retardant polyurethane composite material with low candle wick effect, comprising, by weight, 8 parts of flame-retardant modified glass fiber and 2 parts of resin component; the flame-retardant modified glass fiber is obtained by sequentially performing amino modification and flame-retardant modification on glass fiber; the resin component is composed of the following raw materials by weight: 54 parts of isocyanate, 43 parts of polyol, 2 parts of release agent, and 0 parts of flame retardant. After testing, the flame-retardant grade of the flame-retardant polyurethane composite material is V1.
[0057] A method for preparing a flame-retardant polyurethane composite material with low candle wick effect comprises the following steps:
[0058] Step 1: Processing of glass fiber:
[0059] S1. Amination modification of glass fiber: GF (glass fiber) was dispersed in ethanol / water (500 ml, the mass ratio of ethanol to water was 450:50), and 1 wt% of amino coupling agent (3-aminopropyltriethoxysilane (KH550)) was added under high-speed stirring, and the temperature was raised from room temperature to 80°C for 2 min. After the reaction was completed, the amino-modified glass fiber GF-NH2 was obtained by filtering, washing, and drying at 80°C.
[0060] S2. Preparation of DOPO-PH: 4-aminophenol (10.9 g, 0.1 mole), 4-hydroxybenzaldehyde (12.2 g, 0.1 mole) and methanol were placed in a three-necked round-bottom flask equipped with a magnetic stirrer. The resulting mixture was stirred at 50°C for 5 h under a nitrogen atmosphere. The product 2-[(phenylimino)methyl]phenol was precipitated by adding methanol (200 ml) and cooling the resulting solution with an ice-water bath, and then the solid was separated by filtration and washed with cold methanol. Then, 2-[(phenylimino)methyl]phenol (10 g, 0.05 mole) and DOPO (21.6 g, 0.1 mole) were dissolved in THF (100 ml) at room temperature under a nitrogen atmosphere. The mixture was heated to 60°C and stirred for 12 h. The resulting white precipitate was filtered and washed several times with cold THF, then dried under vacuum, and the white powder was labeled as DOPO-PH.
[0061] S3. Synthesis of GF@DOPO-PH: GF-NH2 was evenly dispersed in ethanol (500 ml, the mass ratio of ethanol to water was 450:50), and DOPO-PH was dissolved in 100 ml of ethanol, and then slowly dripped into the above solution, where DOPO-PH / GF-NH2=3%. After the addition was completed, the reaction was continued for 1 min. After the reaction was completed, it was filtered, washed, and dried at 80°C to obtain the flame retardant modified glass fiber GF@DOPO-PH.
[0062] Step 2: Injecting the resin into the mold through a glue injection machine and mixing it with the flame retardant modified glass fiber in a mass ratio of 7.5:2.5.
[0063] The resin material includes 54 parts of isocyanate, 43 parts of polyol, 2 parts of release agent and 1 part of flame retardant.
[0064] Step three, molding, the mixed system of step two is solidified and molded with a molding mold, and the molding conditions are injection pressure 1Mpa, mold temperature 160°C, 170°C, 180°C, and pultrusion speed 0.5m / min.
[0065] Example 2
[0066] The difference between this embodiment and embodiment 1 is that: in this embodiment, a flame-retardant polyurethane composite material with low candle wick effect includes 8 parts of flame-retardant modified glass fiber and 2 parts of resin component by weight; the flame-retardant modified glass fiber is obtained by sequentially performing amino modification and flame-retardant modification on glass fiber; the resin component is composed of the following raw materials by weight: 53 parts of isocyanate, 42 parts of polyol, 2 parts of release agent, and 3 parts of flame retardant. After testing, the flame retardant grade of the flame-retardant polyurethane composite material is V0.
[0067] Example 3
[0068] The difference between this embodiment and embodiment 1 is that: in this embodiment, a flame-retardant polyurethane composite material with low candle wick effect includes 8 parts of flame-retardant modified glass fiber and 2 parts of resin component by weight; the flame-retardant modified glass fiber is obtained by sequentially performing amino modification and flame-retardant modification on glass fiber; the resin component is composed of the following raw materials by weight: 51 parts of isocyanate, 40 parts of polyol, 2 parts of release agent, and 7 parts of flame retardant. After testing, the flame retardant grade of the flame-retardant polyurethane composite material is MT113.
[0069] Comparative Example 1
[0070] The difference between this comparative example and Example 1 is that in this comparative example, the amount of the flame retardant is 35%.
[0071] Comparative Example 2
[0072] The difference between this comparative example and Example 1 is that in this comparative example, the flame-retardant modified glass fiber is replaced by ordinary glass fiber that has not been modified.
[0073] Comparative Example 3
[0074] The difference between this comparative example and Example 1 is that in this comparative example, only the glass fiber is subjected to amino modification, and no flame retardant modification is performed.
[0075] Comparative Example 4
[0076] The difference between this comparative example and Example 1 is that in this comparative example, only the glass fiber is flame-retardantly modified, and no amino modification is performed.
[0077] Comparative Example 5
[0078] The difference between this comparative example and Example 1 is that in this comparative example, the glass fiber is treated with a conventional flame retardant BDP when the flame retardant modification is performed.
[0079] Comparative Example 6
[0080] The difference between this comparative example and Example 1 is that in this comparative example, when the glass fiber is subjected to amino modification, the coupling agent used is isopropyl tri(dioctyl pyrophosphate) titanate.
[0081] Comparative Example 7
[0082] The difference between this comparative example and Example 1 is that in this comparative example, the flame-retardant modified glass fiber is replaced by ordinary glass fiber that has not been modified, and the amount of the flame retardant is 35%.
[0083] Comparative Example 8
[0084] The difference between this comparative example and Example 1 is that in this comparative example, the flame-retardant modified glass fiber is replaced by ordinary glass fiber without modification, the amount of flame retardant is 35%, and the pultrusion speed is 0.1 m / min.
[0085] Experimental Example 1 Mechanical Properties Test
[0086] The flame retardant modified polyurethane composite materials prepared in the above embodiments and comparative examples were subjected to mechanical property tests, wherein: the mechanical property test method refers to GB / T 3354, the test results are shown in Table 1, and the actual pictures of the composite pultruded products of Embodiment 1 and Comparative Example 1 are shown in Figure 1 , Figure 2 As shown in the figure, it can be seen that adding too much flame retardant in comparative example 1 will affect the curing of the pultruded product, causing the pultruded product to be not completely cured when it leaves the mold, and it will be deformed after being subjected to the pressure of the hydraulic traction machine. Reducing the pressure of the traction machine will cause slippage or even mold blockage.
[0087] Experimental Example 2 Flame retardant performance test
[0088] The flame retardant modified polyurethane composite materials prepared in the above embodiments and comparative examples were tested for flame retardant properties, wherein:
[0089] The flame retardant performance test method refers to GB / T 2408-2008, ASTM D2863 and MT113;
[0090] The experiment was repeated three times in each group, and the results are shown in Table 1: The results show that the use of modified glass fiber can effectively reduce the amount of flame retardant used in composite materials, and can take into account both the mechanical properties and flame retardant properties of the composite materials.
[0091] Table 1
[0092]
[0093] The above is only an embodiment of the present invention, and the common knowledge such as the known specific technical solutions and / or characteristics in the solution is not described in detail here. It should be pointed out that for those skilled in the art, without departing from the technical solution of the present invention, several modifications and improvements can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicality of the patent. The scope of protection required by this application shall be based on the content of its claims, and the specific implementation methods and other records in the specification can be used to interpret the content of the claims.
Claims
1. A flame retardant polyurethane composite material with low candle wick effect, characterized in that: The invention comprises 2-2.5 parts of resin component and 7.5-8 parts of flame retardant modified glass fiber, wherein the resin component is composed of the following raw materials in parts by weight: 51-54 parts of isocyanate, 40-44 parts of polyol, 2 parts of release agent and 0-7 parts of flame retardant; the flame retardant modified glass fiber is obtained by amino-modifying and flame retardant-modifying glass fiber.
2. The flame-retardant polyurethane composite material with low wick effect according to claim 1, characterized in that: The isocyanate is at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate and naphthalene diisocyanate.
3. The flame-retardant polyurethane composite material with low wick effect according to claim 2, characterized in that: The polyol is at least one of polyether polyol, polyester polyol, polyacrylate, and bio-based polyol.
4. The flame-retardant polyurethane composite material with low wick effect according to claim 3, characterized in that: The release agent is at least one of a hydroxy acid-modified polysiloxane internal release agent, an amine-modified polysiloxane internal release agent, a polyether-modified polysiloxane internal release agent, an organic silicon release agent, and an emulsified oil.
5. The flame-retardant polyurethane composite material with low wick effect according to claim 4, characterized in that: The flame retardant is at least one of a phosphorus flame retardant, a bromine flame retardant, a nitrogen flame retardant, and an inorganic flame retardant.
6. The flame-retardant polyurethane composite material with low wick effect according to claim 5, characterized in that: When the glass fiber is subjected to amino modification, the coupling agent used is an amino coupling agent, and the amino coupling agent is at least one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N(2-aminoethyl)3-aminopropylmethoxysilane, and N(2-aminoethyl)3-propylaminomethoxymethylsilane, and the added amount of the amino coupling agent is 1wt%.
7. The flame-retardant polyurethane composite material with low wick effect according to claim 6, characterized in that: When the glass fiber is flame-retardant modified, the flame retardant used is DOPO-PH, and the added amount of DOPO-PH is DOPO-PH / aminated modified glass fiber = 1%-10%.
8. The flame-retardant polyurethane composite material with low wick effect according to claim 7, characterized in that: The structural formula of the DOPO-PH is as shown in formula (1):
9. The flame-retardant polyurethane composite material with low wick effect according to claim 8, characterized in that: The preparation method of DOPO-PH comprises the following steps: S1, mixing 4-aminophenol, 4-hydroxybenzaldehyde and methanol, and stirring to obtain system I; S2, adding methanol to system I and cooling in an ice-water bath to precipitate the product 2-[(phenylimino)methyl]phenol, filtering and separating the solid and washing with cold methanol; S3, dissolving 2-[(phenylimino)methyl]phenol and DOPO in THF, heating and stirring the mixture to obtain System II; S4. The white precipitate in system II was filtered and washed with cold THF, and then dried under vacuum to obtain white powder DOPO-PH.
10. The method for preparing a flame-retardant polyurethane composite material with low wick effect according to any one of claims 1 to 9, characterized in that: The steps include: Step 1: treating the glass fiber: performing amino modification and flame retardant modification on the glass fiber to obtain flame retardant modified glass fiber; Step 2, glue injection: inject the resin into the mold through a glue injection machine and mix it with the flame retardant modified glass fiber. The two are mixed in a mass ratio of 7.5-8:2-2.
5. The resin component is composed of the following raw materials in mass parts: 51-54 parts of isocyanate, 40-44 parts of polyol, 2 parts of release agent, and 0-7 parts of flame retardant; Step 3: Molding: Use a molding mold to perform curing and molding to obtain a flame-retardant polyurethane composite material with low "wick effect".