CN119060398B - Intrinsic flame-retardant polypropylene foam material and preparation method thereof - Google Patents
Intrinsic flame-retardant polypropylene foam material and preparation method thereof Download PDFInfo
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Abstract
本发明公开了一种本征型阻燃聚丙烯发泡材料及其制备方法，包括以下步骤：将聚丙烯粉料、过氧化物引发剂、聚合单体A混匀，通过固相接枝的方法得到接枝1聚合物；将接枝1聚合物和未接枝的聚丙烯粉料混合后通过双螺杆挤出机挤出，在挤出机中段位置通过侧喂料系统添加氨基磷酸酯类阻燃剂进行接枝得到接枝2聚合物；将接枝2聚合物通过高温水蒸气与过量的异氰酸酯基团进行增刚反应；将所得材料进行超临界发泡，得到发泡材料。本发明通过两次接枝加上增刚反应提升材料的熔体强度，并通过超临界流体发泡，整体制备工艺具有清洁环保优势，制备的发泡材料既有氮元素也有磷元素，经测试无卤阻燃效率高，解决了聚丙烯熔体强度低以及阻燃效率低的问题。The present invention discloses an intrinsic flame retardant polypropylene foam material and a preparation method thereof, comprising the following steps: mixing polypropylene powder, peroxide initiator, and polymerization monomer A, obtaining grafted polymer 1 by a solid phase grafting method; mixing grafted polymer 1 and ungrafted polypropylene powder and extruding through a twin-screw extruder, adding aminophosphoric acid ester flame retardant through a side feeding system at the middle position of the extruder for grafting to obtain grafted polymer 2; subjecting grafted polymer 2 to rigidity enhancement reaction with excessive isocyanate groups through high-temperature water vapor; and subjecting the obtained material to supercritical foaming to obtain a foam material. The present invention improves the melt strength of the material through two graftings plus rigidity enhancement reaction, and foams through supercritical fluid. The overall preparation process has the advantages of cleanliness and environmental protection. The prepared foam material has both nitrogen and phosphorus elements. It has high halogen-free flame retardant efficiency after testing, and solves the problems of low melt strength and low flame retardant efficiency of polypropylene.
Description
Technical Field
The invention relates to the technical field of high molecular polymers, in particular to an intrinsic flame-retardant polypropylene foaming material and a preparation method thereof.
Background
The polypropylene is PP for short, is one of four general plastics, has the advantages of low VOC, light weight, excellent mechanical property, stable chemical property and the like, and the material still has good thermal stability and higher mechanical property on the basis of light weight after being foamed. The common foaming mode of PP is supercritical foaming, the supercritical foaming requires PP to have higher melt strength, and the PP is used as a linear polymer, the melt strength of the linear polymer is linearly reduced along with the temperature rise, so that the PP-based material is foamed, and the high melt strength modification is needed.
The foaming PP is widely applied to the fields of new energy batteries, home furnishings, buffer materials and the like at present, and in the application fields, the PP is required to have good flame retardant property, and is subject to a long carbon chain structure of the PP, the PP body is not flame retardant, and flame retardant modification is required.
The current common high melt strength modification mode has the advantages of widening the molecular weight distribution and carbon chain branching technology, introducing ethylene and other comonomers to widen the molecular weight distribution, reducing the physical properties of the material, and easily degrading the material modified by the carbon chain branching technology through screw shearing during post-processing.
The flame retardant modification technology mainly adopts a mode of externally adding a flame retardant at present, the flame retardant can be divided into a halogen-containing flame retardant and a halogen-free flame retardant, the halogen-containing flame retardant is commonly decabromodiphenylethane, octabromoether and the like, and the halogen-containing flame retardant has high molecular polarity and is incompatible with a PP matrix, so that the risk of precipitation can be caused after long-time use, and the halogen-containing flame retardant is gradually replaced along with the enhancement of environmental awareness of people. The halogen-free flame retardant comprises an intumescent flame retardant, nitrogen and phosphorus powder and the like, so that the halogen-free flame retardant needs to be added in a large amount to achieve a flame retardant effect, and the particle size of the halogen-free flame retardant is generally large, so that the halogen-free flame retardant is not easy to disperse in a PP matrix, and large cells can be generated after foaming.
Disclosure of Invention
The invention aims at overcoming the defects in the prior art and provides an intrinsic flame-retardant polypropylene foaming material and a preparation method thereof.
The preparation method of the intrinsic flame-retardant polypropylene foaming material comprises the following steps:
(1) The polypropylene powder, the peroxide initiator and the polymerization monomer A containing double bonds and isocyanate groups are placed in a ball mill to be uniformly mixed, and the graft 1 polymer is obtained by a solid phase grafting method. The ball mill is controlled at 80-140 ℃ and the ball milling time is 0.5-2 h.
The polypropylene powder is preferably homo-polymerization polypropylene, and the particle size of the powder is controlled to be 1-100 microns. The mass ratio of the polypropylene powder to the peroxide initiator is 100:0.2-3, and the mole fraction of double bonds in the polymerized monomer A used by the polypropylene powder per 100 g is 0.1-5%.
The peroxide initiator is selected from lauroyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, tert-butylperoxybenzoate, tert-butylpivalate, di-tert-butylperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p- meng alkane hydroperoxide, and bis (2-phenoxyethyl) peroxydicarbonate.
The polymerization monomer A is selected from vinyl isocyanate, 3-propylene isocyanate, methacrylic acid isocyanate, 2-butene isocyanate, styryl isocyanate, isoprene isocyanate, cyclopentene isocyanate, norbornene isocyanate and methyl styrene isocyanate.
The principle of the reaction of polypropylene, peroxide and polymerized monomer A (vinyl isocyanate) to obtain the graft 1 polymer is as follows:
;
The polypropylene molecular monomer is grafted with isocyanate groups.
(2) Mixing the grafted 1 polymer and ungrafted polypropylene powder according to a certain proportion, extruding by a double-screw extruder, adding phosphoramidate flame retardant at the middle section of the extruder by a side feeding system, and performing secondary grafting reaction by heating and shearing the screw, namely, reacting the amino group of the phosphoramidate flame retardant with the isocyanate group in the grafted 1 polymer to obtain a grafted 2 polymer. The reaction principle is as follows:
;
the mass ratio of the polypropylene powder used in the step (1) to the ungrafted polypropylene powder used in the step (2) is 100:0-50.
The phosphoramidate flame retardant is selected from diphenyl phosphoramidate, tri (2-aminoethyl) phosphate, tri (2-hydroxyethyl) aminomethyl phosphate and diethyl amine phosphate. The amount of the phosphoramidate flame retardant is that the molar ratio of amino groups in the flame retardant to isocyanate groups in the polymer grafted 1 is (55-90) to 100, so that 10% -45% excess of the isocyanate groups is ensured, and isocyanate groups are provided for subsequent stiffening reaction.
(3) And (3) carrying out stiffening reaction on the grafted 2 polymer and excessive isocyanate groups through high-temperature steam to obtain polyurea groups, and improving the melt strength of the material. The stiffening reaction generates CO 2 gas, and the reaction principle is as follows:
;
(4) And (3) performing supercritical foaming on the material obtained in the step (3) to obtain the intrinsic flame-retardant polypropylene foaming material. The supercritical foaming condition is that the temperature of a mould pressing foaming cavity is controlled at 140-160 ℃, the pressure of injected supercritical fluid CO 2 or/and nitrogen is 8-20 MPa, the constant temperature and the constant pressure are 1-4 h, then the pressure is quickly released, the pressure release speed is 1-10 MPa/s, and after the pressure is released to normal pressure, the mould is opened to obtain the foaming material.
The intrinsic flame-retardant polypropylene foaming material is prepared by adopting the preparation method.
The invention has the advantages that:
1. The grafting temperature is controlled below Tm of polypropylene by solid phase grafting of ball milling, and the polypropylene is prevented from being degraded at the temperature of Wen Jiezhi.
2. The amino group of the phosphoramidate flame retardant reacts with the isocyanate group in the polymer of the graft 1 quickly, the grafting efficiency is high in a screw rod, and the side reaction is less.
3. The high melt grafting of polypropylene is to make isocyanate react with water to generate polyurea stiffening on an extrusion line after extruding a screw rod, the stiffening efficiency is high, the formed material is not sheared by the screw rod, the degradation problem of branched materials is avoided, CO 2 is generated in the stiffening process, a gas passage is provided for the subsequent supercritical foaming, and the saturation efficiency in the supercritical foaming is improved.
4. The foaming precursor is foamed by supercritical fluid CO 2 or/and nitrogen, and the whole preparation process has the advantages of cleanness and environmental protection.
5. The invention provides a novel flame-retardant polypropylene foaming material which contains nitrogen element and phosphorus element, has high halogen-free flame-retardant efficiency through testing, and has excellent physical and mechanical properties. The preparation method is novel, and solves the problems of low melt strength and low flame retardant efficiency of polypropylene.
Detailed Description
The embodiment is implemented on the premise of the technical scheme of the invention, and detailed implementation modes and processes are given, but the protection scope of the invention is not limited to the following embodiment. Unless otherwise indicated, the materials used are all commercially available conventional articles.
In an embodiment, the polypropylene used may be T30S、C1608、CP80M、CP80S、EP1X37F、F401、S1004、CF-501、EPS30R、F3002、F400-H、F800E、F800E(DF)、FC801、FC801M、FC801MX、JF300、T36F、X37F、X47F、YPF-3003 or YPF-3008. They are all homo-polypropylene, the particle size of the powder is 1-100 microns.
The peroxide initiator is selected from lauroyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, tert-butylperoxybenzoate, tert-butylpivalate, di-tert-butylperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p- meng alkane hydroperoxide, bis (2-phenoxyethyl) peroxydicarbonate. Their use is the same as that of the examples which list only part of the peroxides.
The polymeric monomer A is selected from vinyl isocyanate, 3-propylene isocyanate, methacrylic acid isocyanate, 2-butylene isocyanate, styrene isocyanate, isoprene isocyanate, cyclopentene isocyanate, norbornene isocyanate and methyl styrene isocyanate. They contain both double bonds and isocyanate groups and the same effect is achieved, examples only listing part of the polymerized monomers A.
The phosphoramidate flame retardant is selected from diphenyl phosphoramidate, tris (2-aminoethyl) phosphate, tris (2-hydroxyethyl) aminomethyl phosphate, and diethyl amine phosphate.
Example 1
100 G polypropylene powder, 0.5 g benzoyl peroxide and 20.7 g vinyl isocyanate are placed in a ball mill for uniform mixing, the temperature of the ball mill is controlled to be 100 ℃, the ball milling time is 0.5 h, and the graft 1 polymer is obtained through a solid phase grafting method.
Mixing the obtained graft 1 polymer with 20 g ungrafted polypropylene powder, extruding by a double-screw extruder, adding 54.82 g diphenyl phosphoramidate at the middle section of the extruder by a side feeding system, and performing secondary grafting reaction by heating and shearing of a screw to obtain the graft 2 polymer.
The grafting 2 polymer is subjected to stiffening reaction and CO 2 gas circuit establishment through high-temperature vapor and excessive isocyanate groups, the speed is 3m per minute, the length of an oven is 12 m, polyurea groups are obtained, and the melt strength of the material is improved. The grafted high-melt intrinsic polypropylene material is respectively injection-molded into solid sheets with the thickness of 4 mm.
And (3) performing supercritical foaming on the solid sheet, controlling the temperature of a mould pressing foaming cavity at 145 ℃, injecting supercritical fluid CO 2 to obtain a pressure of 10 MPa, keeping the temperature and the pressure constant at 2h, rapidly releasing the pressure at 1-10 MPa/s, releasing the pressure to normal pressure, and opening the mould to obtain the intrinsic flame-retardant polypropylene foaming material.
Example 2
100 G polypropylene powder, 1.5 g lauroyl peroxide and 166.2 g of 3-isocyanatopropylene are placed in a ball mill for uniform mixing, the temperature of the ball mill is controlled to be 120 ℃, the ball milling time is 1h, and the graft 1 polymer is obtained through a solid phase grafting method.
And mixing the obtained graft 1 polymer with 30 g ungrafted polypropylene powder, extruding by a double-screw extruder, adding 91.84 g tri (2-aminoethyl) phosphate at the middle section of the extruder by a side feeding system, and performing secondary grafting reaction by heating and shearing by a screw to obtain the graft 2 polymer.
The grafting 2 polymer is subjected to stiffening reaction and CO 2 gas circuit establishment through high-temperature vapor and excessive isocyanate groups, the speed is 3m per minute, the length of an oven is 12 m, polyurea groups are obtained, and the melt strength of the material is improved. The grafted high-melt intrinsic polypropylene material is respectively injection-molded into solid sheets with the thickness of 4 mm.
And (3) performing supercritical foaming on the solid sheet, controlling the temperature of a mould pressing foaming cavity at 150 ℃, injecting supercritical fluid nitrogen at 15 MPa, keeping constant temperature and pressure at 3: 3 h, rapidly releasing pressure at 1-10 MPa/s, releasing pressure to normal pressure, and opening the mould to obtain the intrinsic flame-retardant polypropylene foaming material.
Example 3
100G polypropylene powder, 3 g diisopropyl peroxydicarbonate and 635 g methacrylic acid isocyanate are placed into a ball mill for uniform mixing, the temperature of the ball mill is controlled to be 140 ℃, the ball milling time is 0.8 h, and the graft 1 polymer is obtained through a solid phase grafting method.
Mixing the obtained graft 1 polymer with 50 g ungrafted polypropylene powder, extruding by a double-screw extruder, adding 894 g tri (2-hydroxyethyl) aminomethyl phosphate at the middle section of the extruder by a side feeding system, and performing a secondary grafting reaction by heating and shearing by a screw to obtain the graft 2 polymer.
The grafting 2 polymer is subjected to stiffening reaction and CO 2 gas circuit establishment through high-temperature vapor and excessive isocyanate groups, the speed is 3m per minute, the length of an oven is 12 m, polyurea groups are obtained, and the melt strength of the material is improved. The grafted high-melt intrinsic polypropylene material is respectively injection-molded into solid sheets with the thickness of 4 mm.
And (3) performing supercritical foaming on the solid sheet, controlling the temperature of a mould pressing foaming cavity at 160 ℃, injecting supercritical fluid nitrogen at 8 MPa, keeping constant temperature and constant pressure at 4: 4 h, rapidly releasing pressure at 1-10 MPa/s, releasing pressure to normal pressure, and opening the mould to obtain the intrinsic flame-retardant polypropylene foaming material.
Example 4
100 G polypropylene powder, 0.2 g dicyclohexyl peroxydicarbonate and 13.3 g styryl isocyanate are placed in a ball mill for uniform mixing, the temperature of the ball mill is controlled to be 80 ℃, the ball milling time is 2h, and the graft 1 polymer is obtained by a solid phase grafting method.
And mixing the obtained graft 1 polymer with 40 g ungrafted polypropylene powder, extruding by a double-screw extruder, adding 10.2 g diethyl phosphate amine at the middle section of the extruder by a side feeding system, and carrying out secondary grafting reaction by heating and shearing of a screw to obtain the graft 2 polymer.
The grafting 2 polymer is subjected to stiffening reaction and CO 2 gas circuit establishment through high-temperature vapor and excessive isocyanate groups, the speed is 3m per minute, the length of an oven is 12 m, polyurea groups are obtained, and the melt strength of the material is improved. The grafted high-melt intrinsic polypropylene material is respectively injection-molded into solid sheets with the thickness of 4 mm.
And (3) performing supercritical foaming on the solid sheet, controlling the temperature of a mould pressing foaming cavity at 140 ℃, injecting a mixture of supercritical fluid CO 2 and supercritical fluid nitrogen to 20 MPa, performing constant temperature and constant pressure 1h, performing rapid decompression, performing decompression at the decompression speed of 1-10 MPa/s, and opening the mould after decompression to normal pressure to obtain the intrinsic flame-retardant polypropylene foaming material.
Example 5
100 G polypropylene powder, 2g tert-butyl peroxybenzoate and 146 g methyl styrene isocyanate are placed in a ball mill for uniform mixing, the temperature of the ball mill is controlled to be 110 ℃, the ball milling time is 1.5h, and the graft 1 polymer is obtained through a solid phase grafting method.
Extruding the obtained graft 1 polymer through a double-screw extruder, adding 198 g diphenyl phosphoramidate at the middle section of the extruder through a side feeding system, and carrying out a secondary grafting reaction through heating and shearing of a screw to obtain a graft 2 polymer.
The grafting 2 polymer is subjected to stiffening reaction and CO 2 gas circuit establishment through high-temperature vapor and excessive isocyanate groups, the speed is 3m per minute, the length of an oven is 12 m, polyurea groups are obtained, and the melt strength of the material is improved. The grafted high-melt intrinsic polypropylene material is respectively injection-molded into solid sheets with the thickness of 4 mm.
And (3) performing supercritical foaming on the solid sheet, controlling the temperature of a mould pressing foaming cavity at 155 ℃, injecting supercritical fluid CO 2 at a pressure of 13: 13 MPa, keeping constant temperature and constant pressure of 2.5: 2.5 h, rapidly releasing pressure at a pressure release speed of 1-10: 10 MPa/s, releasing pressure to normal pressure, and opening a mould to obtain the intrinsic flame-retardant polypropylene foaming material.
Example 6
100 G polypropylene powder, 1 g tert-butyl pivalate peroxide and 440 g cyclopentene isocyanate are placed in a ball mill for uniform mixing, the temperature of the ball mill is controlled to be 90 ℃, the ball milling time is 1.8 h, and the graft 1 polymer is obtained through a solid phase grafting method.
And mixing the obtained graft 1 polymer with 10 g ungrafted polypropylene powder, extruding by a double-screw extruder, adding 186 g tri (2-aminoethyl) phosphate at the middle section of the extruder by a side feeding system, and performing secondary grafting reaction by heating and shearing by a screw to obtain the graft 2 polymer.
The grafting 2 polymer is subjected to stiffening reaction and CO 2 gas circuit establishment through high-temperature vapor and excessive isocyanate groups, the speed is 3m per minute, the length of an oven is 12 m, polyurea groups are obtained, and the melt strength of the material is improved. The grafted high-melt intrinsic polypropylene material is respectively injection-molded into solid sheets with the thickness of 4 mm.
And (3) performing supercritical foaming on the solid sheet, controlling the temperature of a mould pressing foaming cavity at 145 ℃, injecting supercritical fluid CO 2 at 17: 17 MPa, maintaining constant temperature and pressure at 1.5: 1.5 h, rapidly releasing pressure at 1-10 MPa/s, releasing pressure to normal pressure, and opening the mould to obtain the intrinsic flame-retardant polypropylene foaming material.
Example 7
100 G polypropylene powder, 2.5 g cumene hydroperoxide and 242.5 g 2-butene isocyanate are placed in a ball mill for uniform mixing, the temperature of the ball mill is controlled to be 130 ℃, the ball milling time is 1.2 h, and the graft 1 polymer is obtained through a solid phase grafting method.
And mixing the obtained graft 1 polymer with 25 g ungrafted polypropylene powder, extruding by a double-screw extruder, adding 342.7 g diphenyl phosphoramidate at the middle section of the extruder by a side feeding system, and performing secondary grafting reaction by heating and shearing of a screw to obtain the graft 2 polymer.
The grafting 2 polymer is subjected to stiffening reaction and CO 2 gas circuit establishment through high-temperature vapor and excessive isocyanate groups, the speed is 3m per minute, the length of an oven is 12 m, polyurea groups are obtained, and the melt strength of the material is improved. The grafted high-melt intrinsic polypropylene material is respectively injection-molded into solid sheets with the thickness of 4 mm.
And (3) performing supercritical foaming on the solid sheet, controlling the temperature of a mould pressing foaming cavity at 150 ℃, injecting supercritical fluid nitrogen at 11 MPa, keeping constant temperature and constant pressure at 3.5: 3.5 h, rapidly releasing pressure at the pressure release speed of 1-10 MPa/s, releasing pressure to normal pressure, and opening the mould to obtain the intrinsic flame-retardant polypropylene foaming material.
Example 8
100 G polypropylene powder, 1.2 g hydrogen peroxide pair meng alkane and 249 g 3-isocyanatopropylene are placed into a ball mill to be uniformly mixed, the temperature of the ball mill is controlled to be 120 ℃, the ball milling time is 1 h, and the graft 1 polymer is obtained through a solid phase grafting method.
Mixing the obtained graft 1 polymer with 15 g ungrafted polypropylene powder, extruding by a double-screw extruder, adding 672.8 g diphenyl phosphoramidate at the middle section of the extruder by a side feeding system, and performing secondary grafting reaction by heating and shearing of a screw to obtain the graft 2 polymer.
The grafting 2 polymer is subjected to stiffening reaction and CO 2 gas circuit establishment through high-temperature vapor and excessive isocyanate groups, the speed is 3m per minute, the length of an oven is 12 m, polyurea groups are obtained, and the melt strength of the material is improved. The grafted high-melt intrinsic polypropylene material is respectively injection-molded into solid sheets with the thickness of 4 mm.
And (3) performing supercritical foaming on the solid sheet, controlling the temperature of a mould pressing foaming cavity at 150 ℃, injecting supercritical fluid CO 2 to obtain a pressure of 14: 14 MPa, keeping constant temperature and constant pressure of 3: 3 h, rapidly releasing pressure at a pressure release speed of 1-10: 10 MPa/s, releasing pressure to normal pressure, and opening the mould to obtain the intrinsic flame-retardant polypropylene foaming material.
Comparative example 1
100 G polypropylene powder, 0.5 g benzoyl peroxide and 20.7 g vinyl isocyanate are placed in a ball mill for uniform mixing, the temperature of the ball mill is controlled to be 100 ℃, the ball milling time is 0.5 h, and the graft 1 polymer is obtained through a solid phase grafting method.
Mixing the obtained graft 1 polymer with 20 g ungrafted polypropylene powder, extruding by a double screw extruder, then carrying out stiffening reaction by high-temperature steam and establishing a CO 2 gas circuit, and controlling the speed of the dryer to be 3 m per minute and the length of the oven to be 12 m. The grafted high-melt polypropylene material is respectively injection-molded into solid sheets with the thickness of 4 mm.
And (3) performing supercritical foaming on the solid sheet, controlling the temperature of a mould pressing foaming cavity at 145 ℃, injecting supercritical fluid CO 2 to 10 MPa, keeping constant temperature and constant pressure at 2h, rapidly releasing pressure at 1-10 MPa/s, releasing pressure to normal pressure, and opening the mould to obtain the polypropylene foaming material.
The difference from example 1 is that no flame retardant grafting was performed.
Comparative example 2
100 G polypropylene powder was extruded through a twin screw extruder, passed through a high temperature steam, vehicle speed 3 m per minute, oven length 12 m, and then the polypropylene material was injection molded into 4 mm thick solid sheets, respectively. Finally, carrying out supercritical foaming on the solid sheet, controlling the temperature of a mould pressing foaming cavity at 145 ℃, injecting supercritical fluid CO 2 to obtain a pressure of 10 MPa, keeping the constant temperature and constant pressure at 2h, then rapidly releasing the pressure at the pressure release speed of 1-10 MPa/s, releasing the pressure to normal pressure, and opening the mould to obtain the polypropylene foaming material.
The difference from example 1 is that no isocyanate group grafting, flame retardant grafting and stiffening reaction was carried out.
Performance testing
The foaming materials prepared in example 1 and comparative example 2 were tested, horizontal flame retardant and vertical flame retardant test method UL94, tensile strength ASTM-D3574-08, bending test method GB-T8812.2-2007, surface rubberizing strength test GB/T33332, and the results are shown in table 1.
Table 1 results of testing the foaming materials of example 1 and comparative example 1, comparative example 2
From the test results, the halogen-free flame retardant containing nitrogen and phosphorus elements is grafted on the molecular chain through complete two grafting reactions and one stiffening reaction in the embodiment 1, the solid sheet can be vertically combusted through V-0, and meanwhile, the flame retardant grade of the foamed material can reach V-1, and compared with the comparative example 2, the flame retardant has the advantages of improved tensile property, improved melt strength and improved flame retardant property. In comparative example 1, since the raw material still contains nitrogen element in the first grafting, the solid sheet still has a certain flame retardant grade, and after the solid sheet is subjected to stiffening reaction, the stiffening effect is good because the isocyanate group content in the molecular chain is high, the tensile strength and the melt strength are higher than those of example 1, and the density of the obtained material is higher under the same foaming condition. Both example 1 and comparative example 1 underwent foaming reaction, and the surface had more bubbles, so that the surface-coating peeling force showed an upward trend after foaming. The comparative example 2 has poor physical and mechanical properties without grafting and stiffening reaction, and cannot meet the melt strength required by supercritical foaming, and the pure material has no flame retardant effect.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Claims (8)
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| CN104356305A (en) * | 2014-10-30 | 2015-02-18 | 徐州工业职业技术学院 | A method for preparing high melt strength polypropylene based on solid phase grafting |
| CN112759827A (en) * | 2019-10-21 | 2021-05-07 | 国家能源投资集团有限责任公司 | Flame-retardant polypropylene composition, flame-retardant foamed polypropylene and preparation method thereof |
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| CN101125947A (en) * | 2007-08-01 | 2008-02-20 | 浙江大学 | High melt strength polypropylene containing long-chain branched structure and its preparation method |
| CN102863588A (en) * | 2011-07-08 | 2013-01-09 | 中国石油天然气股份有限公司 | A method for supercritical carbon dioxide assisted solid-phase grafting modified polypropylene |
| CN102558449A (en) * | 2011-12-13 | 2012-07-11 | 金发科技股份有限公司 | High-melt-strength polypropylene material, and preparation method and application thereof |
| WO2014002958A1 (en) * | 2012-06-28 | 2014-01-03 | 大八化学工業株式会社 | Flame retarding agent, flame-retardant aqueous resin composition and flame-retardant urethane resin composition containing said flame retarding agent, and use therefor |
| WO2017023613A1 (en) * | 2015-07-31 | 2017-02-09 | Lubrizol Advanced Materials, Inc. | Guanylurea alcohol phosphates and their use as reactants in polyurethane and epoxy resin applications |
| CN108239241B (en) * | 2016-12-27 | 2020-03-13 | 金发科技股份有限公司 | Graft copolymer containing isocyanate group and application thereof |
| CN116444922B (en) * | 2023-03-06 | 2024-07-02 | 江苏昊晟塑业科技有限公司 | Flame-retardant polymer foam material for automobiles and preparation method thereof |
| CN116606474B (en) * | 2023-05-08 | 2024-02-09 | 扬州斯帕克实业有限公司 | Preparation method of flame-retardant polypropylene foam material |
| CN118359837B (en) * | 2024-06-19 | 2024-08-16 | 浙江新恒泰新材料股份有限公司 | High-resilience polyolefin foam material and preparation method thereof |
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| CN104356305A (en) * | 2014-10-30 | 2015-02-18 | 徐州工业职业技术学院 | A method for preparing high melt strength polypropylene based on solid phase grafting |
| CN112759827A (en) * | 2019-10-21 | 2021-05-07 | 国家能源投资集团有限责任公司 | Flame-retardant polypropylene composition, flame-retardant foamed polypropylene and preparation method thereof |
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