CN101514254B - Sheet molding compound with high flame resistance, low smoke and non-toxic and preparation method thereof - Google Patents
Sheet molding compound with high flame resistance, low smoke and non-toxic and preparation method thereof Download PDFInfo
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- CN101514254B CN101514254B CN2009100793483A CN200910079348A CN101514254B CN 101514254 B CN101514254 B CN 101514254B CN 2009100793483 A CN2009100793483 A CN 2009100793483A CN 200910079348 A CN200910079348 A CN 200910079348A CN 101514254 B CN101514254 B CN 101514254B
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Abstract
The invention relates to a sheet molding compound with high flame resistance, low smoke and non-toxic and a preparation method thereof. The formula of the sheet molding compound comprises the following substance in mass portion: 50-80 portions of unsaturated polyester resin, 15-60 portions of low shrink additive, 1-3 portions of evocating agent, 0.01-0.05 portions of polymerization inhibitor, 0.7-7 portions of wetting and dispersing agent, 3-8 potions of inner mold release agent, 1-2 potions of thickening agent, 20-50 potions of viscosity reduction filler, 100-200 portions of flame retardant A, 50-100 portions of flame retardant B and 50-250 portions of reinforced material; the flame retardant A is micron aluminum hydroxide and the grain diameter is 0.4-3.5 microns; the flame retardant B is nanometer aluminum hydroxide and the grain diameter is 30-80 nanometers. The sheet molding compound of the invention has the advantages of high flame resistance, low smoke and non-toxic, well mechanical performance and surface decorative effect.
Description
Technical field
The present invention relates to the chemical raw material field, particularly a kind of sheet molding compound with high flame resistance, low smoke and non-toxic and preparation method thereof.
Background technology
The vehicles and large-scale public place, the finishing material of especially large-scale track traffic inside require not only that it is high-strength, lightweight, comfortable, good decorating effect, and more emphasize to decorate the security with the facility material.Along with market continues extensive development, the sheet molding compound pressing has obtained using widely, the flame retardant properties of this built-in material lay special stress on its security, especially material, so the sheet molding compound pressing has all carried out fire-retardant finish to starting material in process of production.Fire-retardant finish to material generally adopts following several method at present: the one, adopt Halogen or phosphorated fire retardant, generally the covet fire performance of material of this method, but goods are in case burning just can be because of Halogen or phosphorous a large amount of toxic gas and the smog of producing, and people's life security is caused and infringement greatly; The 2nd, add filling aluminium hydrate in a large number, the advantage of this method is to improve the fire performance and the control cigarette poison of material simultaneously, but its shortcoming is a large amount of ordinary hydrogen alumina packings that add, can cause the surface quality and the mechanical property of goods to descend significantly, lost its lightweight, high-strength characteristic, be damaged thereby make to decorate or arrange easily.
Summary of the invention
In order to overcome deficiency of the prior art, the invention provides a kind of high flame resistance, low smoke toxicity, the sheet molding compound with high flame resistance, low smoke and non-toxic material that has favorable mechanical performance and surface decoration effect again simultaneously.
Another object of the present invention provides above-mentioned sheet molding compound with high flame resistance, low smoke and non-toxic preparation methods.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of sheet molding compound with high flame resistance, low smoke and non-toxic, and the prescription of described plastics comprises following materials in parts by mass:
50～80 parts of unsaturated polyester resins, 15～60 parts of low shrinkage additives, 1～3 part of initiator, 0.01～0.05 part of stopper, 0.7～7 part of wetting dispersing agent, 3～8 parts of inner pattern releasing agent applicables, 1～2 part of thickening material, 20～50 parts of viscosity reduction fillers, fire retardant A100～200 part, fire retardant B50～100 part, strongthener 50-250 part; Described fire retardant A is a micron order aluminium hydroxide, and its particle diameter is 0.4～3.5 micron, and described fire retardant B is a nano level aluminium hydroxide, and particle diameter is 30～80 nanometers.
Described unsaturated polyester resin contains the special-purpose unsaturated polyester resin of the sheet molding compound of holding carboxyl, described low shrinkage additive is selected from one or more in the compatible type additive of vibrin, described initiator is selected from one or more in the organo-peroxide, described stopper is selected from one or more in the derivative of substituted phenol, described wetting dispersing agent is selected from BYK-W9010, BYK-W996, BYK-W995, among the BYK-W990 one or more, described inner pattern releasing agent applicable is selected from one or more in the Metallic stearates, described thickening material is one or both mixing in high dispersive magnesium oxide or the magnesium hydroxide, described viscosity reduction filler is one or more in the thixotropic filler, and described strongthener is the short alkali-free glass fibre yarn of cutting.
The compatible type additive of described vibrin is saturated polyester, polyethylene powder, polystyrene, thermoplastic polyester or polyvinyl acetate (PVA), described organo-peroxide is peroxidized t-butyl perbenzoate, tert-butyl hydroperoxide-2-ethylhexanoate or 1, the 1-cyclohexane di-tert-butyl peroxide, the derivative of described substituted phenol is benzoquinones, Pyrogentisinic Acid, 2,6 di-t-butyls-4-sylvan or quinhydrones, described Metallic stearates is calcium stearate, zinc stearate or stearic acid aluminium, and described thixotropic filler is aerosil, WE polyethylene wax or organobentonite.
The present invention also provides a kind of preparation method of sheet molding compound with high flame resistance, low smoke and non-toxic, may further comprise the steps:
(1) low shrinkage additive, initiator, stopper, wetting dispersing agent, inner pattern releasing agent applicable, thickening material are added is equipped with in the stirring tank of unsaturated polyester resin, be stirred to and be uniformly dispersed;
(2) add viscosity reduction filler and fire retardant A again, stir so that the speed of 400-600 commentaries on classics/min is powerful;
(3) open ultrasonic powerful emulsification instrument, add fire retardant B, stir, obtain disperseing the unsaturated polyester of homogeneous to stick with paste through brute force;
(4) be barrier film with polyethylene film, dipping 25mm strongthener on sheet molding compound (SMC) sheet material unit, after the roll-in rolling, thickening is deposited.
1, adopts the viscosity reduction filler, utilize its thixotropy, increase the add-on of aluminium hydroxide flame-retardant filler;
2, adopt nano level aluminium hydroxide to mix use, improve flame retardant resistance, reduce smoke toxicity with micron order aluminium hydroxide flame-retardant filler;
3, adopt ultrasonic hybrid technique, the nano level filling aluminium hydrate can be dispersed in the resin system.
With compare in the prior art, the present invention adopts the beneficial effect of technique scheme to be:
1, passenger train of the present invention adopts the special-purpose unsaturated polyester resin system of SMC with sheet molding compound with high flame resistance, low smoke and non-toxic; Utilize modified Nano aluminium hydroxide,, by ultrasonic dispersing technology dispersing and mixing nano-aluminum hydroxide filler, nano level aluminium hydroxide is fully disperseed in resin paste simultaneously by the aluminium hydroxide fineness grating of improving; Thereby the fire-retardant and smoking property of material is greatly improved, makes it reach the fire-retardant requirement of relevant regulations such as DIN5510, UIC564, the Ministry of Railways.
2, the present invention adopts the aluminium hydroxide of different fineness grade as composite flame-retardant agent, join aluminium hydroxide in the polymkeric substance and reduced the concentration of flammable polymeric matrix, thereby reduce the heat release rate of flame-retardant system, crystal water absorbs a large amount of heat and dewaters when material is heated simultaneously; Generate activated alumina behind the aluminium hydroxide dehydration, generate protection charcoal layer, reduced flame-retardant system smog growing amount.
3, nano-aluminum hydroxide adds as filler, can fully improve micron order filling aluminium hydrate tap density, can improve its surface quality, can improve the toughness of goods again; Nano-aluminum hydroxide is as the part of fire retardant, and its adding helps to give full play to the flame retardant properties of aluminium hydroxide.Tiny because of nano-particles size, specific surface area is big, particle under the homodisperse situation, can evenly discharge its flame retardant resistance when goods are heated in polymeric material, nanoparticle is well dispersed in the micron order aluminium hydroxide carbon skeleton, can make protective layer finer and close.
Embodiment
The present invention is described in further detail below by specific embodiment.Below each embodiment be only used for the explanation rather than the restriction the present invention.
Embodiment 1
Take by weighing material (kg) according to following quality:
Unsaturated polyester resin 80kg, low shrinkage additive 20kg, initiator 1.5kg, stopper 0.02kg, wetting dispersing agent 4kg, inner pattern releasing agent applicable 4kg, thickening material 1kg, viscosity reduction filler 20kg, fire retardant A180kg, fire retardant B60kg, strongthener 92kg.
The preparation method:
With low shrinkage additive 20kg, initiator 1.5kg, stopper 0.02kg, wetting dispersing agent 6kg, inner pattern releasing agent applicable 4kg, thickening material 1kg adds to be had in the stirring tank of unsaturated polyester resin 80kg, is stirred to be uniformly dispersed; Add viscosity reduction filler 20kg, fire retardant A180kg, the powerful stirring; Open ultrasonic powerful emulsification instrument, add fire retardant B60kg, stir, obtain disperseing the unsaturated polyester of homogeneous to stick with paste through brute force.With polyethylene film is barrier film, the short alkali-free glass fibre yarn of cutting of dipping 25mm on general SMC sheet material unit, and weak point is cut alkali-free glass fibre yarn 92kg, and after the roll-in rolling, thickening is deposited.
In the foregoing description, unsaturated polyester resin is P17-951 (production of Nanjing DSM resin company limited), low shrinkage additive is saturated polyester H852-903 (production of Nanjing DSM resin company limited), initiator is a peroxidized t-butyl perbenzoate, stopper is the Pyrogentisinic Acid, wetting dispersing agent is BYK-W996 (German Bi Ke company produce), inner pattern releasing agent applicable is a Zinic stearas, the viscosity reduction filler is an aerosil, fire retardant A is aluminium hydroxide ON-904 (U.S. refined precious chemical industry company limited produces), fire retardant B is that (size-grade distribution 20～50nm), strongthener is the short alkali-free glass fibre yarn of cutting to nano-aluminum hydroxide.
This embodiment product properties sees the following form 1:
| Sequence number | Performance perameter | Unit | Numerical value | Standard |
| 1 | Density | kg/m 3 | 1.82 | GB?1463 |
| 2 | Barcol hardness | / | 61 | GB?3854 |
| 3 | Tensile strength | MPa | 118 | GB?1447 |
| 4 | Flexural strength | MPa | 157 | GB?1449 |
| 5 | Shock strength | KJ/m2 | 99 | GB?1451 |
| 6 | Water-intake rate | ％ | 0.2 | GB?1462 |
| 7 | H?DT | ℃ | 200 | GB?1634 |
| 8 | Oxygen index | ％ | 44 | GB?8924 |
| 9 | Smoke density (D4) | ? | 7 | GB?8323 |
| 10 | The 45 burning | Class | Extremely difficult combustion | TB/T?2402 |
| 11 | Combustionproperty | Class | S?4 | DIN?5510 |
| 12 | Smoking property | Class | SR?2 | DIN?5510 |
| 13 | The melts drippage | Class | ST?2 | DIN?5510 |
| 14 | Burst size of methanal | mg/L | ≤0.1 | GB?18580 |
Embodiment 2
Take by weighing material (kg) according to following quality:
Unsaturated polyester resin 75kg, low shrinkage additive 30kg, initiator 1.5kg, stopper 0.04kg, wetting dispersing agent 3.5kg, inner pattern releasing agent applicable 6kg, thickening material 2kg, viscosity reduction filler 40kg, fire retardant A150kg, fire retardant B50kg, strongthener 143kg.
Preparation method such as embodiment 1;
In the foregoing description, unsaturated polyester resin is P17-902 (production of Nanjing DSM resin company limited), low shrinkage additive is polystyrene H814-901 (production of Nanjing DSM resin company limited), initiator is tert-butyl hydroperoxide-2-ethylhexanoate, stopper is a benzoquinones, wetting dispersing agent is BYK-W990, inner pattern releasing agent applicable is a calcium stearate, the viscosity reduction filler is an organobentonite, fire retardant A is aluminium hydroxide ON-906 (U.S. refined precious chemical industry company limited produces), fire retardant B is that (size-grade distribution 20～50nm), strongthener is the short alkali-free glass fibre yarn of cutting to nano-aluminum hydroxide.
This embodiment product properties sees the following form 2:
| Sequence number | Performance perameter | Unit | Numerical value | Standard |
| 1 | Density | kg/m 3 | 1.88 | GB?1463 |
| 2 | Barcol hardness | / | 63 | GB?3854 |
| 3 | Tensile strength | MPa | 138 | GB?1447 |
| 4 | Flexural strength | MPa | 177 | GB?1449 |
| 5 | Shock strength | KJ/m2 | 110 | GB?1451 |
| 6 | Water-intake rate | ％ | 0.2 | GB?1462 |
| 7 | H?DT | ℃ | 205 | GB?1634 |
| 8 | Oxygen index | ％ | 39 | GB?8924 |
| 9 | Smoke density (D4) | ? | 20 | GB?8323 |
| 10 | The 45 burning | Class | Extremely difficult combustion | TB/T?2402 |
| 11 | Combustionproperty | Class | S?4 | DIN?5510 |
| 12 | Smoking property | Class | SR?2 | DIN?5510 |
| 13 | The melts drippage | Class | ST?2 | DIN?5510 |
| 14 | Burst size of methanal | mg/L | ≤0.1 | GB?18580 |
Embodiment 3
Take by weighing material (kg) according to following quality:
Unsaturated polyester resin 75kg, low shrinkage additive 20kg, initiator 1kg, stopper 0.01kg, wetting dispersing agent 5kg, inner pattern releasing agent applicable 5kg, thickening material 1kg, viscosity reduction filler 30kg, fire retardant A180kg, fire retardant B100kg, strongthener 83kg.
Preparation method such as embodiment 1;
In the foregoing description, unsaturated polyester resin is P17-901 (production of Nanjing DSM resin company limited), low shrinkage additive is thermoplastic resin H870-902, initiator is tert-butyl hydroperoxide-2-ethylhexanoate, stopper is a benzoquinones, wetting dispersing agent is BYK-W990, inner pattern releasing agent applicable is a calcium stearate, the viscosity reduction filler is WE polyethylene wax 10g, aerosil 20g, fire retardant A is aluminium hydroxide ON-904 (U.S. refined precious chemical industry company limited produces), fire retardant B is that (size-grade distribution 20～50nm), strongthener is the short alkali-free glass fibre yarn of cutting to nano-aluminum hydroxide.
This embodiment product properties sees the following form 3:
| Sequence number | Performance perameter | Unit | Numerical value | Standard |
| 1 | Density | kg/m 3 | 1.78 | GB?1463 |
| 2 | Barcol hardness | / | 60 | GB?3854 |
| 3 | Tensile strength | MPa | 108 | GB?1447 |
| 4 | Flexural strength | MPa | 127 | GB?1449 |
| 5 | Shock strength | KJ/m2 | 89 | GB?1451 |
| 6 | Water-intake rate | ％ | 0.2 | GB?1462 |
| 7 | H?DT | ℃ | 190 | GB?1634 |
| 8 | Oxygen index | ％ | 52 | GB?8924 |
| 9 | Smoke density (D4) | ? | 6 | GB?8323 |
| 10 | The 45 burning | Class | Extremely difficult combustion | TB/T?2402 |
| 11 | Combustionproperty | Class | S?4 | DIN?5510 |
| 12 | Smoking property | Class | SR?2 | DIN?5510 |
| 13 | The melts drippage | Class | ST?2 | DIN?5510 |
| 14 | Burst size of methanal | mg/L | ≤0.1 | GB?18580 |
Claims (4)
1. a sheet molding compound with high flame resistance, low smoke and non-toxic is characterized in that, the prescription of described moulding compound comprises following materials in parts by mass:
50～80 parts of unsaturated polyester resins, 15～60 parts of low shrinkage additives, 1～3 part of initiator, 0.01～0.05 part of stopper, 0.7～7 part of wetting dispersing agent, 3～8 parts of inner pattern releasing agent applicables, 1～2 part of thickening material, 20～50 parts of viscosity reduction fillers, fire retardant A100～200 part, fire retardant B50～100 part, strongthener 50-250 part; Described fire retardant A is a micron order aluminium hydroxide, and its particle diameter is 0.4～3.5 micron, and described fire retardant B is a nano level aluminium hydroxide, and particle diameter is 30～80 nanometers.
2. a kind of sheet molding compound with high flame resistance, low smoke and non-toxic according to claim 1, it is characterized in that, described unsaturated polyester resin contains the special-purpose unsaturated polyester resin of the sheet molding compound of holding carboxyl, described low shrinkage additive is selected from one or more in the compatible type additive of vibrin, described initiator is selected from one or more in the organo-peroxide, described stopper is selected from one or more in the derivative of substituted phenol, described wetting dispersing agent is selected from BYK-W9010, BYK-W996, BYK-W995, among the BYK-W990 one or more, described inner pattern releasing agent applicable is selected from one or more in the Metallic stearates, described thickening material is one or both mixing in high dispersive magnesium oxide or the magnesium hydroxide, described viscosity reduction filler is one or more in the thixotropic filler, and described strongthener is the short alkali-free glass fibre yarn of cutting.
3. a kind of sheet molding compound with high flame resistance, low smoke and non-toxic according to claim 2, it is characterized in that, the compatible type additive of described vibrin is the polyethylene powder, polystyrene, thermoplastic polyester or polyvinyl acetate (PVA), described organo-peroxide is a peroxidized t-butyl perbenzoate, tert-butyl hydroperoxide-2-ethylhexanoate or 1, the 1-cyclohexane di-tert-butyl peroxide, the derivative of described substituted phenol is a benzoquinones, the Pyrogentisinic Acid, 2,6 di-t-butyls-4-sylvan or quinhydrones, described Metallic stearates is a calcium stearate, zinc stearate or stearic acid aluminium, described thixotropic filler is an aerosil, WE polyethylene wax or organobentonite.
4. according to the preparation method of each described sheet molding compound with high flame resistance, low smoke and non-toxic of claim 1-3, it is characterized in that, may further comprise the steps:
(1) low shrinkage additive, initiator, stopper, wetting dispersing agent, inner pattern releasing agent applicable, thickening material are added is equipped with in the stirring tank of unsaturated polyester resin, be stirred to and be uniformly dispersed;
(2) add viscosity reduction filler and fire retardant A again, stir so that the speed of 400-600 commentaries on classics/min is powerful;
(3) open ultrasonic powerful emulsification instrument, add fire retardant B, stir, obtain disperseing the unsaturated polyester of homogeneous to stick with paste through brute force;
(4) be barrier film with polyethylene film, dipping 25mm strongthener on sheet molding compound sheet material unit, after the roll-in rolling, thickening is deposited.
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| CN2009100793483A CN101514254B (en) | 2009-03-09 | 2009-03-09 | Sheet molding compound with high flame resistance, low smoke and non-toxic and preparation method thereof |
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| CN2009100793483A CN101514254B (en) | 2009-03-09 | 2009-03-09 | Sheet molding compound with high flame resistance, low smoke and non-toxic and preparation method thereof |
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| CN101514254B true CN101514254B (en) | 2011-12-14 |
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