CN113845624B - Sheet molding compound, preparation method thereof and sheet molding compound product - Google Patents
Sheet molding compound, preparation method thereof and sheet molding compound product Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- C08F263/00—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00
- C08F263/02—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00 on to polymers of vinyl esters with monocarboxylic acids
- C08F263/04—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00 on to polymers of vinyl esters with monocarboxylic acids on to polymers of vinyl acetate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K3/2279—Oxides; Hydroxides of metals of antimony
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- C08K3/32—Phosphorus-containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
- C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
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- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
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- C08K7/14—Glass
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K7/16—Solid spheres
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- 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
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
- C08K7/20—Glass
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- 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
Abstract
The invention provides a sheet molding compound, which comprises a resin composition and a reinforcement, wherein the resin composition comprises the following components in parts by weight: unsaturated polyester resin: 35-50 parts of low shrinkage agent: 5-15 parts of initiator: 1-3 parts of a diluent monomer: 15-70 parts of a cross-linked network regulator: 0.5-30 parts; wherein the crosslinking network regulator is alpha-methyl styrene linear dimer and C 5‑14 One or more of aliphatic thiols and thiol derivatives thereof. The sheet molding compound containing the crosslinking network regulator with specific content can be used for preparing sheet molding compound products with uniform crosslinking network structure and low VOC value. The invention also provides a sheet molding compound product and a preparation method thereof.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a sheet molding compound, a preparation method thereof and a sheet molding compound product.
Background
Sheet Molding Compounds (SMC) are important molding materials for molding processes, and automotive parts such as automotive upholsteries are often prepared from sheet molding compounds. The common sheet molding compound on the market is mainly formed by using unsaturated polyester resin as a matrix and crosslinking and polymerizing the unsaturated polyester resin with diluted monomers such as styrene and the like, a crosslinked network structure of a sheet molding compound product formed by curing the sheet molding compound is not uniform, grids of a part of the crosslinked network are compact, volatile small molecules such as benzene and styrene are difficult to escape, and a large amount of organic small molecules are remained, so that a high VOC (low volatile organic compound) value is caused, and the strict requirement of an automobile part on low VOC cannot be met.
Disclosure of Invention
In view of the above, the invention provides a sheet molding compound, a preparation method thereof and a sheet molding compound product, so as to solve the problems of non-uniform cross-linked network structure and excessively high VOC value of the conventional sheet molding compound product.
In a first aspect, the present invention provides a sheet molding compound, the raw materials of which include a resin composition and a reinforcement, wherein the resin composition includes the following components in parts by weight:
unsaturated polyester resin: 35-50 parts of (by weight),
low shrinkage agent: 5-15 parts of (A) a stabilizer,
initiator: 1-3 parts of (A) a solvent,
diluting monomers: 15-70 parts of (A) and (B),
cross-linked network modifier: 0.5-30 parts; wherein the crosslinking network regulator is alpha-methyl styrene linear dimer and C 5-14 One or more of aliphatic thiols and thiol derivatives thereof.
In the present invention, the above resin composition and the reinforcement may be stored separately. The sheet molding compound is obtained by curing a sheet formed by compounding the resin composition and the reinforcement, wherein the resin composition can infiltrate the reinforcement. Optionally, in the sheet molding compound, the reinforcement is 80 to 120 parts by weight. Further, the weight ratio of the resin composition to the reinforcement is (0.5-4): 1.
alternatively, the reinforcement may be selected from at least one of glass fiber, carbon fiber, and aramid fiber. Preferably, the reinforcement is glass fiber. The bonding force between the glass fiber reinforcement and the unsaturated polyester resin in the resin composition is strong, so that the sheet molding compound product made of the sheet molding compound has higher strength. Further optionally, the length of the reinforcement is 15-60mm.
In the present invention, the unsaturated polyester resin may contain unsaturated groups such as carbon-carbon double bonds, carbon-carbon triple bonds, benzene rings, and the like. Alternatively, the unsaturated polyester resin may be selected from at least one of ortho-benzene type unsaturated polyester resin, meta-benzene type unsaturated polyester resin, bisphenol a type unsaturated polyester resin, and halogenated unsaturated polyester resin. In the present invention, the solid content of the unsaturated polyester resin is 100%. Preferably, the unsaturated polyester resin is an o-benzene type unsaturated polyester resin. The resin has low cost and good mechanical properties such as stretchability, bendability and the like.
Alternatively, the diluent monomer may be selected from at least one of styrene, methyl styrene, and acrylate monomers (e.g., methyl methacrylate, butyl methacrylate, etc.). Preferably, the diluent monomer is styrene, which has low cost, strong diluting capability and strong copolymerization activity with unsaturated polyester resin.
In the invention, in the compression molding process of the sheet molding compound, the unsaturated polyester resin and the diluent monomer in the raw material of the sheet molding compound are subjected to cross-linking polymerization under the initiation of an initiator. Optionally, the initiator is an organic peroxide initiator. Specifically, the initiator may be at least one selected from tert-butyl peroxy-2-ethylhexyl carbonate (also referred to as initiator TBEC), tert-butyl peroxy-2-ethylhexanoate (abbreviated as TBPO), and tert-butyl peroxybenzoate (abbreviated as TBPB), but is not limited thereto.
In the present invention, the crosslinking network modifier may be at least one of an α -methylstyrene linear dimer, a thiol compound, and the like.
Wherein the structural formula of the alpha-methyl styrene linear dimer is shown as
CAS number 6362-80-7, the side group macromolecular structure thereof has larger steric hindrance effect, and can provide steric hindrance in the compression molding process of sheet molding compound under heating, avoid entanglement among molecular chains, reduce local densification of cross-linked network, and make cross-linkingThe network as a whole tends to be uniform.
Wherein the thiol compound comprises C 5-14 One or more of aliphatic thiols and thiol derivatives thereof. Specifically, C 5-14 The aliphatic thiol is an aliphatic thiol having 5 to 14 carbon atoms, and examples thereof include primary decathiol, primary dodecanethiol, n-dodecanethiol, tertiary octanethiol, and tertiary hexadecanethiol. For C 5-14 Examples of the aliphatic thiol derivative include at least one of n-dodecylmercaptane acetate, mono-n-dodecylmercaptane succinate, di-n-dodecylmercaptane oxalate, n-dodecylmercaptane benzoate, sodium mono-n-dodecylmercaptane sulfate, tri-n-dodecylthiomethane, di-n-dodecyl trithiocarbonate, 1-n-dodecylthiotrichloro alcohol and β -phenyl- β -n-dodecylthioethylphenyl ketone.
Preferably, the weight part of the crosslinking network regulator is 1 to 10 parts. More preferably 4 to 10 parts.
In the invention, the low shrinkage agent is used for reducing the shrinkage rate of the sheet molding compound in the compression molding process so as to improve the apparent effect of the obtained sheet molding compound product, so that the surface of the sheet molding compound product is smooth and flat, and the degree of matching with the shape of a mold used in the compression molding process is extremely high. Alternatively, the low shrinkage agent may be selected from at least one of polystyrene, polyvinyl acetate, polymethyl methacrylate, polyethylene terephthalate, and adipic acid. Preferably, the low profile agent is polyvinyl acetate. In the present invention, the solid content of the low shrinkage agent is 100%.
Optionally, the resin composition further comprises an additive including at least one of a thickener, a mold release agent, a low-density filler, a flame retardant, a wetting agent, a polymerization inhibitor, and the like.
According to the invention, the addition of the low-density filler can play a good weight reduction effect, so that the density of the sheet molding compound product is reduced, the molding shrinkage and the thermal expansion rate of resin can also be reduced, the sheet molding compound product is prevented from generating cracks or fissures, and the stability of the product is ensured. Wherein the density of the low-density fillerAt 1g/cm 3 The following. Alternatively, the low-density filler may be at least one of glass beads, expandable microspheres, and the like.
Further optionally, the low-density filler is present in the sheet molding compound in an amount of 10 to 40 parts by weight. Preferably 20 to 30 parts. Preferably, the low-density filler is glass beads. The glass beads in parts by weight can play a weight-reducing effect and adjust the viscosity of the resin composition, so that the resin composition can well infiltrate the reinforcement body, and the phase separation of the unsaturated polyester resin and the low shrinkage agent is avoided.
Further optionally, in the sheet molding compound, the flame retardant is 10 to 60 parts by weight. For example, 30 to 40 parts and 10 to 28 parts. In the present invention, the flame retardant is used to impart flame retardant properties to articles made from the sheet molding compound. Wherein the flame retardant may be selected from at least one of decabromodiphenylethane, antimony trioxide, aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate, melamine uronate, and melamine, but is not limited thereto.
Preferably, the flame retardant is decabromodiphenylethane and antimony trioxide, so that the flame retardant property of the sheet molding compound product is more effectively improved, and the mechanical strength of the sheet molding compound product is not influenced. More preferably, the weight ratio of the decabromodiphenylethane to the antimony trioxide is (2-5): 1, the flame retardant with less dosage can ensure that the sheet molding compound product has the flame retardant performance with higher flame retardant grade, and the reduction of the dosage of the flame retardant means that the dosage of the low-density filler can be properly increased to reduce the density of the sheet molding compound product, so that the sheet molding compound product has good flame retardant performance and low density.
Further optionally, the thickener is present in an amount of 1 to 5 parts by weight of the sheet molding compound. In the invention, the thickening agent can perform physical crosslinking reaction with the unsaturated polyester resin, so that the uniformity and the fluidity of the resin composition are ensured, and the strength of a sheet molding compound product is further ensured. Optionally, the thickener is selected from at least one of magnesium oxide, magnesium hydroxide, calcium oxide and calcium hydroxide, but is not limited thereto. Preferably, the thickener is magnesium oxide.
Further optionally, in the sheet molding compound, the mold release agent is in an amount of 3 to 6 parts by weight. The addition of the release agent can be beneficial to the stripping of the sheet molding compound from the mold, and the phenomenon of mold sticking is avoided. Alternatively, the release agent may be selected from at least one of stearic acid, zinc stearate, calcium stearate, and magnesium stearate. Preferably, the release agent is zinc stearate.
Further optionally, the wetting agent is present in the sheet molding compound in an amount of 0.1 to 4 parts by weight. In the invention, the addition of the wetting agent can further adjust the viscosity of the resin composition, improve the compatibility among the components, realize good infiltration on the reinforcement, reduce the stress defect of the sheet molding compound product and ensure that the sheet molding compound product has good mechanical property. Alternatively, the wetting agent may be selected from at least one of BYK-W-9010, BYK-W-9012, BYK-W-996, BYK-W-995, and the like, but is not limited thereto.
Further optionally, in the sheet molding compound, the polymerization inhibitor is 0.02 to 0.1 part by weight. The addition of the polymerization inhibitor can capture a part of free radicals, thereby prolonging the gelation time of the resin composition and also playing a role in prolonging the shelf life of the resin paste. Optionally, the polymerization inhibitor is selected from at least one of phenol, hydroquinone, t-butylcatechol, 2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-methylphenol, methylhydroquinone, p-benzoquinone, tetrachlorobenzoquinone, l, 4-naphthoquinone, and p-hydroxyanisole. Preferably, the polymerization inhibitor is p-benzoquinone and/or 2,6-di-tert-butyl-4-methylphenol.
In one embodiment of the present invention, the resin composition comprises the following components in parts by weight: unsaturated polyester resin: 35-50 parts of low shrinkage agent: 5-15 parts of initiator: 1-3 parts of a diluent monomer: 15-70 parts of a cross-linked network regulator: 0.5-30 parts of thickening agent: 1-5 parts of a release agent: 3-6 parts of low-density filler: 0-40 parts of flame retardant: 0-60 parts, wetting agent: 0-6 parts of polymerization inhibitor: 0 to 0.1 portion.
The sheet molding compound provided by the first aspect of the invention contains the crosslinking network regulator with a specific content, so that a sheet molding compound product formed by molding the sheet molding compound has a good crosslinking network structure, all crosslinking points are uniformly distributed, a grid is uniform and proper in size, no part of over-tight crosslinking points exists, small molecular substances such as benzene, toluene, styrene and the like can well escape in the curing process, and the VOC value is very low.
Accordingly, the second aspect of the present invention also provides a method for preparing a sheet molding compound product, comprising the steps of:
the preparation method comprises the following steps of uniformly mixing unsaturated polyester resin, a low shrinkage agent, an initiator, a diluent monomer and a crosslinking network regulator to obtain a resin composition, wherein the resin composition comprises the following components in parts by weight: unsaturated polyester resin: 35-50 parts of low shrinkage agent: 5-15 parts of initiator: 1-3 parts of a diluent monomer: 15-70 parts of a cross-linked network regulator: 0.5-30 parts; wherein the crosslinking network regulator is alpha-methyl styrene linear dimer and C 5-14 One or more of aliphatic thiols and thiol derivatives thereof;
preparing the resin composition and the reinforcement into a sheet, and curing the sheet to obtain a sheet molding compound; and carrying out compression molding on the sheet molding compound to obtain a sheet molding compound product.
In the invention, the unsaturated polyester resin, the low shrinkage agent, the initiator, the diluent monomer and the crosslinking network regulator can be added and mixed together or can be added separately. In one embodiment of the present invention, the resin composition may be prepared by: unsaturated polyester resin, low shrinkage agent and diluent monomer are mixed first, and then initiator and crosslinking network regulator are added.
Optionally, the resin composition further comprises an additive, wherein the additive comprises at least one of a thickening agent, a mold release agent, a low-density filler, a flame retardant, a wetting agent and a polymerization inhibitor. The amounts and effects of the above components are as described in the first aspect of the present invention and will not be described herein again. Wherein, if the additive contains the thickening agent, the thickening agent is added finally, the obtained resin composition is immediately compounded with the reinforcement to prepare a sheet material, and the sheet molding compound is obtained through aging treatment. Therefore, the reinforcing body can be ensured to be fully soaked, and the mechanical property of the sheet molding compound product is improved.
In another embodiment of the present invention, the resin composition can be obtained by the following method: firstly, uniformly mixing unsaturated polyester resin, a low shrinkage agent and a diluent monomer to obtain first slurry; and adding an initiator, a crosslinking network regulator and other additives (such as at least one of a wetting agent, a polymerization inhibitor, a release agent, a low-density filler and a flame retardant) except the thickening agent into the first slurry, uniformly mixing, and finally adding the thickening agent to obtain the resin composition. In other embodiments of the present invention, after the first slurry is obtained, other components may be added in sequence (each time one component is added, and after mixing is performed, the other component is added), as long as the thickener is added at last.
Alternatively, the resin composition and the reinforcement are made into a sheet by the following steps: and impregnating the reinforcement body with the resin composition on a sheet molding compound unit, compacting, rolling and forming into a sheet. Further, the obtained sheet may be hermetically packaged for later aging and storage.
Optionally, the temperature of the curing treatment is 35-45 ℃, and the time of the curing treatment is 24-72h. In the present invention, the object of the aging treatment is to thicken the sheet to give a sheet molding compound of a desired viscosity and to maintain this viscosity state smoothly during long-term storage.
Optionally, the temperature for compression molding is 130-180 ℃. For example 140-160 deg.c. Optionally, the compression molding is carried out at a molding pressure of 5 to 20MPa, for example 5 to 15 or 6 to 10MPa. Optionally, the compression molding time is 1-15min, preferably 3-10min.
Optionally, C of said sheet molding plastic article 6 -C 16 The content of volatile organic compounds is less than or equal to 1000 mu g/m 3 。
Optionally, the sheet molding compound article has a tensile strength of 50 to 130MPa. Preferably 70-130MPa. More preferably 120 to 130MPa.
The preparation method of the sheet molding compound product provided by the second aspect of the invention has simple and controllable process, uniform cross-linked network structure of the prepared sheet molding compound product and low content of volatile organic compounds.
The third aspect of the invention also provides a sheet molding compound product, which is prepared by the preparation method of the sheet molding compound product.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
A method of making a sheet molding plastic article, comprising:
(1) Putting 40 parts of unsaturated polyester resin (specifically, o-phenyl unsaturated polyester resin), 15 parts of low shrinkage agent (specifically, polyvinyl acetate) and 30 parts of diluent monomer (specifically, styrene) into stirring equipment in parts by weight, and uniformly stirring to obtain first slurry;
adding 1.5 parts of initiator (specifically 2-ethylhexyl tert-butyl carbonate peroxide), 10 parts of cross-linked network regulator (specifically alpha-methyl styrene linear dimer), 0.05 part of polymerization inhibitor (specifically p-benzoquinone), 4.5 parts of release agent (specifically zinc stearate), 25 parts of glass beads, 40 parts of flame retardant (30 parts of decabromodiphenylethane and 10 parts of antimony trioxide) and 3 parts of wetting agent (specifically BYK-W-9010) into the first slurry, uniformly stirring, finally adding 2.5 parts of thickener (specifically magnesium oxide), and uniformly stirring to obtain a pasty resin composition;
(2) Carrying out composite impregnation on the resin composition and 100 parts of glass fiber on a sheet machine, and then compacting, rolling, sealing, packaging and the like to prepare a sheet; then placing the sheet into a curing chamber for curing treatment, wherein the curing temperature is 40 ℃, and the curing time is 48 hours, so as to prepare the sheet molding compound;
(3) And (3) carrying out compression molding on the sheet molding compound to prepare a sheet molding compound product, wherein the compression molding temperature is 140 ℃, the compression molding pressure is 15MPa, and the compression molding time is 10min.
Example 2
In contrast to example 1, the part by weight of the crosslinked network modifier was 2 parts.
Example 3
Unlike example 1, the crosslinked network modifier was present in 6 parts by weight.
Example 4
Unlike example 1, 10 parts by weight of a thiol compound (specifically, n-dodecyl mercaptan) was used as the crosslinking network modifier.
Example 5
Unlike example 1, the flame retardant was 60 parts by weight of aluminum hydroxide, and the glass beads were 5 parts by weight.
Example 6
Unlike example 1, the flame retardant was 40 parts by weight of aluminum hydroxide.
Example 7
A method of making a sheet molding plastic article, comprising:
(1) Putting 50 parts by weight of unsaturated polyester resin (specifically bisphenol A type unsaturated polyester resin), 30 parts by weight of low shrinkage agent (specifically polyethylene terephthalate) and 40 parts by weight of diluent monomer (specifically styrene) into stirring equipment, and uniformly stirring to obtain first slurry;
adding 2 parts of initiator (specifically tert-butyl peroxybenzoate), 8 parts of crosslinking network regulator (specifically alpha-methyl styrene linear dimer), 0.1 part of polymerization inhibitor (specifically hydroquinone), 5 parts of release agent (specifically zinc stearate), 5 parts of low-density filler (specifically expandable microspheres), 20 parts of flame retardant (specifically ammonium polyphosphate) and 2 parts of wetting agent (specifically BYK-W-9012) into the first slurry, uniformly stirring, finally adding 2 parts of thickener (specifically magnesium oxide), and uniformly stirring to obtain a pasty resin composition;
(2) Carrying out composite impregnation on the resin composition and 100 parts of glass fiber on a sheet machine, and then compacting, rolling, sealing, packaging and the like to prepare a sheet; then placing the sheet into a curing chamber for curing treatment, wherein the curing temperature is 40 ℃, and the curing time is 48 hours, so as to prepare the sheet molding compound;
(3) And (3) carrying out compression molding on the sheet molding compound to prepare a sheet molding compound product, wherein the compression molding temperature is 140 ℃, the compression molding pressure is 15MPa, and the compression molding time is 10min.
To highlight the beneficial effects of the present invention, comparative example 1 is provided, wherein comparative example 1 differs from example 1 in that: no alpha-methylstyrene linear dimer was added.
And (3) testing the VOC content: the sheet molding compound articles of example 1 and comparative example 1 were subjected to VOC testing in accordance with the Q/BYDQ-A1901.771-2017 standard. As a result, it was found that the sheet molding plastic article of example 1 had a content of C6-C16 volatile organic compounds of 483. Mu.g/m 3 The sheet molding compound of comparative example 1 had a C6-C16 VOC content of up to 5522g/m 3 This indicates that the addition of a specific amount of cross-linking network modifier during the preparation of the sheet molding compound results in a lower VOC value of the final sheet molding compound article.
The sheet molding compounds of examples 1 to 3 of the present invention and comparative example 1 were subjected to at least the following performance tests:
1. and (3) testing tensile strength: testing the sheet molding compound product according to the GB 8410-2006 standard;
2. and (3) testing the VOC content: testing the content of low Volatile Organic Compounds (VOC) of the sheet molding compound product according to the Q/BYDQ-A1901.771-2017 standard;
3. and (3) testing the flame retardant property: testing the flame retardant rating of the sheet molding compound product according to UL 94-2017 clause 8;
4. and (3) testing the density: the sheet molding compound articles were subjected to density testing in accordance with GB 8410-2006 standard.
The results of the performance testing of each sheet molding compound article are summarized in Table 1 below.
TABLE 1 Performance test results for sheet molding plastic articles
As can be seen from Table 1, the VOC content of the sheet molding plastic articles of the examples of the present invention using the crosslinked network modifier was lower, much lower than that of the comparative example 1, in which the crosslinked network modifier was not used. Wherein, in examples 5-6, compared with example 1, the flame retardant used in examples 5-6 is not a mixture of decabromodiphenylethane and antimony trioxide, and the amount of the flame retardant used in the prepared sheet molding compound product is relatively large when the flame retardant property is slightly lower, and the amount of the low-density filler, i.e., glass beads, is correspondingly reduced, so that the density of the sheet molding compound product is relatively high (example 5); when the same parts by weight of other flame retardants were used in the sheet molding compound product, the flame retardant properties of the sheet molding compound product were greatly reduced (example 6).
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (15)
1. The sheet molding compound is characterized in that raw materials of the sheet molding compound comprise a resin composition and a reinforcement, wherein the resin composition comprises the following components in parts by weight:
unsaturated polyester resin: 35-50 parts of (A) a solvent,
low shrinkage agent: 5-15 parts of (A) a stabilizer,
initiator: 1-3 parts of (by weight),
diluting monomers: 15-70 parts of (A) and (B),
cross-linked network modifier: 0.5-30 parts; wherein the crosslinking network regulator is alpha-methyl styrene linear dimer and C 5-14 Aliphatic thiolsOne or more of the derivatives; wherein, the C 5-14 The aliphatic mercaptan derivative includes at least one of n-dodecylmercaptan acetate, mono-n-dodecylmercaptan succinate, di-n-dodecylmercaptan oxalate, n-dodecylmercaptan benzoate, sodium mono-n-dodecylsulfanyl sulfate, tri-n-dodecylsulfanyl methane, di-n-dodecyl trithiocarbonate, 1-n-dodecylsulfanyl trichloro-ethanol, and β -phenyl- β -n-dodecylsulfanyl ethyl phenyl ketone.
2. The sheet molding compound of claim 1, wherein the weight fraction of said reinforcement is 80-120 parts; the reinforcement is selected from at least one of glass fiber, carbon fiber and aramid fiber.
3. The sheet molding compound as claimed in claim 1, wherein said unsaturated polyester resin is at least one selected from the group consisting of ortho-benzene type unsaturated polyester resin, meta-benzene type unsaturated polyester resin, bisphenol A type unsaturated polyester resin and halogenated unsaturated polyester resin; the diluent monomer is at least one selected from styrene, methyl styrene and acrylate monomers.
4. The sheet molding compound of claim 1, wherein said low profile agent is selected from at least one of polystyrene, polyvinyl acetate, polymethyl methacrylate, polyethylene terephthalate, and adipic acid; the initiator is at least one selected from tert-butyl peroxy-2-ethylhexyl carbonate, tert-butyl peroxy-2-ethylhexanoate and tert-butyl peroxybenzoate.
5. The sheet molding compound of any one of claims 1-4, wherein said resin composition further comprises an additive comprising at least one of a thickener, a mold release agent, a low density filler, a flame retardant, a wetting agent, and a polymerization inhibitor.
6. The sheet molding compound of claim 5, wherein said low-density filler is present in said sheet molding compound in an amount of from 10 to 40 parts by weight; the low-density filler is selected from at least one of glass micro-beads and expandable micro-spheres.
7. The sheet molding compound of claim 5, wherein said flame retardant is present in said sheet molding compound in an amount of 10 to 60 parts by weight; the flame retardant is at least one selected from decabromodiphenylethane, antimony trioxide, aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate, melamine uronate and melamine.
8. The sheet molding compound of claim 7, wherein said flame retardant is decabromodiphenylethane and antimony trioxide, wherein the weight ratio of decabromodiphenylethane to antimony trioxide is (2-5): 1.
9. the sheet molding compound of claim 5, wherein said thickener is present in said sheet molding compound in an amount of 1 to 5 parts by weight; the thickener is at least one selected from magnesium oxide, magnesium hydroxide, calcium oxide and calcium hydroxide.
10. The sheet molding compound of claim 5, wherein said mold release agent is present in said sheet molding compound in an amount of 3 to 6 parts by weight; the release agent may be selected from at least one of stearic acid, zinc stearate, calcium stearate, and magnesium stearate.
11. The sheet molding compound of claim 5, wherein said wetting agent is present in said sheet molding compound in an amount of 0.1 to 4 parts by weight.
12. The sheet molding compound of claim 5, wherein said polymerization inhibitor is present in an amount of 0.02 to 0.1 parts by weight.
13. A method for preparing a sheet molding compound product is characterized by comprising the following steps:
the preparation method comprises the following steps of uniformly mixing unsaturated polyester resin, a low shrinkage agent, an initiator, a diluent monomer and a crosslinking network regulator to obtain a resin composition, wherein the resin composition comprises the following components in parts by weight: unsaturated polyester resin: 35-50 parts of low shrinkage agent: 5-15 parts of initiator: 1-3 parts of a diluent monomer: 15-70 parts of a cross-linked network regulator: 0.5-30 parts; wherein the crosslinking network regulator is alpha-methyl styrene linear dimer and C 5-14 One or more of aliphatic thiol derivatives; wherein, the C 5-14 The aliphatic mercaptan derivative comprises at least one of n-dodecyl mercaptan acetate, mono-n-dodecyl mercaptan succinate, di-n-dodecyl mercaptan oxalate, n-dodecyl mercaptan benzoate, mono-n-dodecyl sulfanyl sodium sulfate, tri-n-dodecylsulfanyl methane, di-n-dodecyl trithiocarbonate, 1-n-dodecylsulfanyl trichloro alcohol and beta-phenyl-beta-n-dodecylsulfanyl ethyl phenyl ketone;
preparing the resin composition and the reinforcement into a sheet, and curing the sheet to obtain a sheet molding compound; and carrying out compression molding on the sheet molding compound to obtain a sheet molding compound product.
14. The method of claim 13, wherein the resin composition further comprises the following additives in parts by weight: thickening agent: 1-5 parts of a release agent: 3-6 parts of low-density filler: 0-40 parts of flame retardant: 0-60 parts, wetting agent: 0-6 parts of polymerization inhibitor: 0 to 0.1 portion.
15. A sheet molding compound article, characterized in that it is produced by the method for producing a sheet molding compound according to any one of claims 13 to 14 or by the sheet molding compound according to any one of claims 1 to 12.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996000753A1 (en) * | 1994-06-30 | 1996-01-11 | Nippon Zeon Co., Ltd. | Unsaturated polyester resin composition and process for molding said composition |
| CN109957134A (en) * | 2017-12-22 | 2019-07-02 | 比亚迪股份有限公司 | A kind of SMC resin combination, its composite material and its composite material and preparation method thereof |
| CN111019312A (en) * | 2019-12-26 | 2020-04-17 | 世泰仕塑料有限公司 | Low-VOC sheet molding compound and production process thereof |
| CN111171540A (en) * | 2020-02-03 | 2020-05-19 | 武汉理工大学 | Low-density low-pressure sheet molding compound and preparation method thereof |
| CN111978477A (en) * | 2019-05-24 | 2020-11-24 | 比亚迪股份有限公司 | Sheet molding compound raw material, sheet molding compound product, and preparation method and application thereof |
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2020
- 2020-06-28 CN CN202010598886.XA patent/CN113845624B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996000753A1 (en) * | 1994-06-30 | 1996-01-11 | Nippon Zeon Co., Ltd. | Unsaturated polyester resin composition and process for molding said composition |
| CN109957134A (en) * | 2017-12-22 | 2019-07-02 | 比亚迪股份有限公司 | A kind of SMC resin combination, its composite material and its composite material and preparation method thereof |
| CN111978477A (en) * | 2019-05-24 | 2020-11-24 | 比亚迪股份有限公司 | Sheet molding compound raw material, sheet molding compound product, and preparation method and application thereof |
| CN111019312A (en) * | 2019-12-26 | 2020-04-17 | 世泰仕塑料有限公司 | Low-VOC sheet molding compound and production process thereof |
| CN111171540A (en) * | 2020-02-03 | 2020-05-19 | 武汉理工大学 | Low-density low-pressure sheet molding compound and preparation method thereof |
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