CN108724853B - Preparation method of halogen-free intumescent flame-retardant glass fiber reinforced polypropylene plate - Google Patents

Preparation method of halogen-free intumescent flame-retardant glass fiber reinforced polypropylene plate Download PDF

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CN108724853B
CN108724853B CN201810397154.7A CN201810397154A CN108724853B CN 108724853 B CN108724853 B CN 108724853B CN 201810397154 A CN201810397154 A CN 201810397154A CN 108724853 B CN108724853 B CN 108724853B
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glass fiber
halogen
flame retardant
intumescent flame
polypropylene
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CN108724853A (en
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朱红芳
韩立尚
娄晓
田科巍
陈蓬勃
杨正高
陈钢
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Polyrocks Chemical Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions
    • B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/20—All layers being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B32B2260/023—Two or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

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  • Polymers & Plastics (AREA)
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  • Fluid Mechanics (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention discloses a preparation method of a halogen-free intumescent flame-retardant glass fiber reinforced polypropylene plate. The preparation method comprises the steps of uniformly scattering the halogen-free intumescent flame retardant on the surface of the polypropylene pre-impregnated glass fiber felt, overlapping at least three layers of the polypropylene pre-impregnated glass fiber felt scattered with the halogen-free intumescent flame retardant, and performing hot press molding to obtain the halogen-free intumescent flame-retardant glass fiber reinforced polypropylene plate. The invention directly spreads the powder fire retardant on the surface of the polypropylene pre-impregnated glass fiber felt, and then adopts the hot press molding process to directly compound the glass fiber polypropylene pre-impregnated thermoplastic composite board in a multilayer way. The prepared polypropylene prepreg thermoplastic composite board has excellent mechanical property and flame retardant property.

Description

Preparation method of halogen-free intumescent flame-retardant glass fiber reinforced polypropylene plate
Technical Field
The invention relates to a preparation method of a halogen-free intumescent flame-retardant glass fiber reinforced polypropylene plate.
Background
The glass fiber polypropylene prepreg thermoplastic composite board (GMT) is compounded at a certain pressure and temperature by using a polypropylene fiber and glass fiber blended glass fiber felt as a main reinforcing framework and using a polypropylene film and a hot melt adhesive film as a sizing agent and an adhesive. Has a series of advantages of high strength, small density, good low-temperature toughness, good heat resistance, small molding shrinkage and the like, and is widely applied in the automobile manufacturing industry.
Due to the glass fiber wick effect, the flame retardant difficulty of GMT products is high, and the general solution is to prepare a polypropylene film and a hot melt adhesive film into a flame retardant polypropylene film or a flame retardant hot melt adhesive film, prepare polypropylene fibers into flame retardant polypropylene fibers, and then compound the flame retardant polypropylene fibers with a glass fiber felt. The modified particle of the flame-retardant polypropylene is required to be prepared into a film by blowing or tape casting, and the modified particle of the flame-retardant polypropylene is also prepared into polypropylene fiber by wire drawing. The choice of flame retardant is very limited due to the blowing, casting and drawing processes. In CN1807497A, ammonium polyphosphate, melamine and pentaerythritol are adopted to prepare an expandable flame retardant, then the expandable flame retardant, polypropylene, an antioxidant and the like are plasticized and granulated, then mixed with glass fiber, polypropylene and the like, and then molded or extruded into a sheet shape and molded with a glass fiber felt to form a glass fiber reinforced polypropylene flame retardant composite material. CN103374174A, CN107129631A, CN106147019A, CN100419018C, CN102417661A and the like are all prepared into composite materials after mixing and granulating flame retardant, different auxiliaries and polypropylene, and the expandable flame retardant has the characteristics of overlong heating time, complex process flow and the like. CN103950251A sprays halogen-free flame retardant powder and adhesive glue solution on a thin felt made of reinforced fibers and thermoplastic resin, then winds the thin felt into an intermediate felt through pre-needling and main needling, then carries out tentering oven curing, then sends the intermediate felt into a heat engine for hot pressing, and finally qualitatively prepares the flame-retardant light fiber reinforced thermoplastic resin composite material through a cold pressing roller. The method is relatively simple and easy to implement, but for GMT manufacturers, needling felting equipment is required, and the application of the method in the industry is limited.
Disclosure of Invention
The invention aims to provide a preparation method of a halogen-free intumescent flame-retardant glass fiber reinforced polypropylene plate.
The technical scheme adopted by the invention is as follows:
a preparation method of a halogen-free intumescent flame retardant glass fiber reinforced polypropylene plate comprises the steps of uniformly scattering halogen-free intumescent flame retardant on the surface of a polypropylene pre-impregnated glass fiber felt, overlapping at least three layers of the polypropylene pre-impregnated glass fiber felt scattered with the halogen-free intumescent flame retardant, and performing hot press molding to obtain the halogen-free intumescent flame retardant glass fiber reinforced polypropylene plate.
In the preparation method, the glass fiber mass content of the polypropylene pre-impregnated glass fiber felt is 15-70%, the breadth of the polypropylene pre-impregnated glass fiber felt is less than or equal to 2m, and the gram weight of the polypropylene pre-impregnated glass fiber felt is 600g/m2～1800g/m2。
In the preparation method, the quality of the halogen-free intumescent flame retardant sprinkled on each layer of the polypropylene pre-impregnated glass fiber felt is the same.
In the preparation method, the addition amount of the halogen-free intumescent flame retardant accounts for 10-30% of the mass percent of the polypropylene pre-impregnated glass fiber felt.
In the preparation method, the halogen-free intumescent flame retardant consists of the following raw materials in percentage by mass: 40% -75% of an acid source; 15% -50% of a carbon source; 0.5 to 10 percent of synergistic agent.
In the halogen-free intumescent flame retardant of the preparation method, the acid source is at least one of ammonium polyphosphate, melamine polyphosphate and organic phosphinate; the carbon source is at least one of pentaerythritol, dipentaerythritol and expandable graphite; the synergist is at least one of aluminum hydroxide, magnesium hydroxide, melamine cyanurate, zinc borate and zinc chloride.
In the preparation method, the hot-press molding conditions are as follows: the temperature is 120-230 ℃, the pressure is 5-20 MPa, and the time is 20-120 seconds.
The invention has the beneficial effects that:
the invention directly spreads the powder fire retardant on the surface of the polypropylene pre-impregnated glass fiber felt, and then adopts the hot press molding process to directly compound the glass fiber polypropylene pre-impregnated thermoplastic composite board in a multilayer way. The prepared polypropylene prepreg thermoplastic composite board has excellent mechanical property and flame retardant property, and can meet the requirements of flame retardant properties of interior materials of JTT1905-2016 operation passenger cars on interior plates, luggage compartment coverings, floor base materials and other interior materials.
Detailed Description
A preparation method of a halogen-free intumescent flame retardant glass fiber reinforced polypropylene plate comprises the steps of uniformly scattering halogen-free intumescent flame retardant on the surface of a polypropylene pre-impregnated glass fiber felt, overlapping at least three layers of the polypropylene pre-impregnated glass fiber felt scattered with the halogen-free intumescent flame retardant, and performing hot press molding to obtain the halogen-free intumescent flame retardant glass fiber reinforced polypropylene plate.
Preferably, in the preparation method, the glass fiber mass content of the polypropylene pre-impregnated glass fiber felt is 15-70%, the width of the polypropylene pre-impregnated glass fiber felt is less than or equal to 2m, and the gram weight of the polypropylene pre-impregnated glass fiber felt is 600g/m2～1800g/m2。
Preferably, in the preparation method, the quality of the halogen-free intumescent flame retardant sprinkled on each layer of the polypropylene prepreg glass fiber felt is the same.
Preferably, in the preparation method, the addition amount of the halogen-free intumescent flame retardant accounts for 10-30% of the mass percent of the polypropylene pre-impregnated glass fiber felt.
Preferably, in the preparation method, the halogen-free intumescent flame retardant consists of the following raw materials in percentage by mass: 40% -75% of an acid source; 15% -50% of a carbon source; 0.5 to 10 percent of synergistic agent.
Preferably, in the halogen-free intumescent flame retardant of the preparation method, the acid source is at least one of ammonium polyphosphate, melamine polyphosphate and organic phosphinate; further preferably, the acid source is ammonium polyphosphate.
Preferably, in the halogen-free intumescent flame retardant of the preparation method, the carbon source is at least one of pentaerythritol, dipentaerythritol and expandable graphite; further preferably, the carbon source is at least one of pentaerythritol and expandable graphite.
Preferably, in the halogen-free intumescent flame retardant prepared by the preparation method, the synergist is at least one of aluminum hydroxide, magnesium hydroxide, melamine cyanurate, zinc borate and zinc chloride; further preferably, the synergist is zinc borate.
Further preferably, the halogen-free intumescent flame retardant consists of the following raw materials in percentage by mass: ammonium polyphosphate 50% -60%; 25% -35% of expandable graphite; 8 to 15 percent of pentaerythritol; 0.5 to 2 percent of zinc borate.
Preferably, in the preparation method, the conditions of hot press molding are as follows: the temperature is 120-230 ℃, the pressure is 5-20 MPa, and the time is 20-120 seconds.
The present invention will be described in further detail with reference to specific examples. The starting materials used in the examples are, unless otherwise specified, commercially available from conventional sources.
Example 1:
206 g of ammonium polyphosphate, 124 g of expandable graphite, 41.2 g of pentaerythritol and 4.12 g of zinc borate are mixed uniformly, and then the mixture is taken out and divided into three equal parts, wherein each part is about 125 g. Uniformly spreading each part of flame retardant at a width of 0.5m, a length of 0.67m and a gram weight of 1500g/m2The surface of polypropylene pre-impregnated glass fiber felt with the glass fiber content of 40 wt% is superposed and stacked, then is put into a die press at the temperature of 150 ℃ and the pressure of 10MPa for die pressing for 60 seconds, is taken out, is cooled and is cut into the flame-retardant glass fiber feltThe sample strip is tested to have an oxygen index of 30, a vertical burning rate of less than or equal to 20mm/min and a horizontal burning rate of A-0.
Example 2:
150 g of ammonium polyphosphate, 99 g of expandable graphite, 45 g of pentaerythritol and 6 g of zinc borate are uniformly mixed, and then the mixture is taken out and divided into three equal parts, wherein each part is 100 g. Uniformly spreading each part of flame retardant at a width of 1m, a length of 0.8m and a gram weight of 600g/m2The method comprises the following steps of superposing and stacking three layers of polypropylene pre-impregnated glass fiber felts with flame retardant powder on the surface of a polypropylene pre-impregnated glass fiber felt with the glass fiber content of 30 wt%, putting the three layers of polypropylene pre-impregnated glass fiber felts into a die press at the temperature of 130 ℃ and under the pressure of 15MPa for die pressing for 50 seconds, taking out the three layers of polypropylene pre-impregnated glass fiber felts, cooling the three layers of polypropylene pre-impregnated glass fiber felts, cutting the three layers of polypropylene pre-impregnated glass fiber felts into flame retardant sample strips, and testing.
Example 3:
170 g of ammonium polyphosphate, 85 g of expandable graphite, 40 g of pentaerythritol and 5 g of zinc borate are uniformly mixed, and then the mixture is taken out and divided into three equal parts, wherein each part is 100 g. Uniformly spreading each part of flame retardant at a width of 0.8m, a length of 0.5m and a gram weight of 1800g/m2The surface of a polypropylene pre-impregnated glass fiber felt with the glass fiber content of 60 wt% is superposed and stacked, the three layers of polypropylene pre-impregnated glass fiber felts with the flame retardant powder are placed into a die press at the temperature of 200 ℃ and under the pressure of 8MPa for die pressing for 80 seconds and then taken out, the materials are cut into flame-retardant sample strips after cooling, and the test shows that the oxygen index is 32, the vertical burning rate is not more than 30mm/min, and the horizontal burning rate is A-0.

Claims (2)

1. A preparation method of a halogen-free intumescent flame-retardant glass fiber reinforced polypropylene plate is characterized by comprising the following steps: uniformly scattering halogen-free intumescent flame retardant on the surface of the polypropylene pre-impregnated glass fiber mat, overlapping at least three layers of the polypropylene pre-impregnated glass fiber mats scattered with the halogen-free intumescent flame retardant, and performing hot press molding to obtain a halogen-free intumescent flame retardant glass fiber reinforced polypropylene plate;
the glass fiber mass content of the polypropylene pre-impregnated glass fiber felt is 15% -70%, the width of the polypropylene pre-impregnated glass fiber felt is less than or equal to 2m, and the gram weight of the polypropylene pre-impregnated glass fiber felt is 600g/m2～1800g/m2；
The addition amount of the halogen-free intumescent flame retardant accounts for 10-30% of the mass percent of the polypropylene pre-impregnated glass fiber felt;
the halogen-free intumescent flame retardant consists of the following raw materials in percentage by mass: 40% -75% of an acid source; 15% -50% of a carbon source; 0.5 to 10 percent of synergist;
in the halogen-free intumescent flame retardant, the acid source is at least one of ammonium polyphosphate, melamine polyphosphate and organic phosphinate; the carbon source is at least one of pentaerythritol, dipentaerythritol and expandable graphite; the synergist is at least one of aluminum hydroxide, magnesium hydroxide, melamine cyanurate, zinc borate and zinc chloride;
the hot press molding conditions are as follows: the temperature is 120-230 ℃, the pressure is 5-20 MPa, and the time is 20-120 seconds.
2. The preparation method of the halogen-free intumescent flame retardant glass fiber reinforced polypropylene plate as claimed in claim 1, wherein the preparation method comprises the following steps: the quality of the halogen-free intumescent flame retardant scattered in each layer of the polypropylene pre-impregnated glass fiber felt is the same.
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WO1999003792A1 (en) * 1997-07-17 1999-01-28 Nu-Chem, Inc. Methods of making high-temperature glass fiber and thermal protective structures
CN1257784A (en) * 1998-12-21 2000-06-28 国碳科技股份有限公司 Method for making fire-resistant fabrics and its products
CN102532681A (en) * 2010-12-14 2012-07-04 上海杰事杰新材料(集团)股份有限公司 Halogen-free flame-retardant continuous fiber reinforced polypropylene composite material and preparation method thereof
CN102492218A (en) * 2011-11-29 2012-06-13 深圳市科聚新材料有限公司 Halogen-free expansion type flame-retardant glass fiber reinforced polypropylene material and preparation method thereof
CN105061896A (en) * 2015-08-20 2015-11-18 贵州大学 Halogen-free flame-retardant LGFPP (long glass fiber reinforced polypropylene) material and preparation method thereof

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