CN104371237A - Unsaturated polyester resin composition thickened by non-alkali metal systems and bulk molding compound with unsaturated polyester resin composition - Google Patents
Unsaturated polyester resin composition thickened by non-alkali metal systems and bulk molding compound with unsaturated polyester resin composition Download PDFInfo
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Abstract
The invention discloses an unsaturated polyester resin composition thickened by non-alkali metal systems and a bulk molding compound with the unsaturated polyester resin composition. By the aid of the unsaturated polyester resin composition and the bulk molding compound, the problem of easiness in solid-liquid phase separation when existing molding compounds are heated and stressed and flow mainly can be solved. A plurality of types of unsaturated polyester resin are matched with one another to form a body of the composition. The unsaturated polyester resin composition is characterized by comprising the modified unsaturated polyester resin. The unsaturated polyester resin composition and the bulk molding compound have the advantages that the stability of the molding compound can be effectively improved owing to special effects of the modified unsaturated polyester resin and particle sizes and proportions of preferable inorganic fillers, the unsaturated polyester resin composition is not thickened by the traditional alkali metal systems, accordingly, pre-mixing and follow-up curing viscosity control procedures and the like and expensive viscosity reducers and impregnating compounds can be omitted, and energy consumption of production equipment can be reduced; the bulk molding compound can be manufactured by the aid of a compression molding technology, a transfer molding technology and an injection molding technology, and a manufactured molded product is excellent in thin-walled appearance and mechanical strength as compared with an equivalent product thickened by alkali metal systems.
Description
Technical field
The present invention relates to the technical field of thermoset glass matrix material in macromolecular material, be specially unsaturated polyester resin compositions and the Bulk Molding Compound thereof of the thickening of a kind of non-alkali metal system.
Background technology
Along with the develop rapidly of domestic electric utility technology, in case for circuit breaker, the shortcoming of a large amount of traditional material such as bakelite and pottery adopted was appeared in one's mind day by day in the past, and the index such as physical strength, electric durability energy, dimensional stability as the former can not meet the product requirement improved constantly; Although and the latter's stable chemical nature, have hard and crisp, the easy insoluble problem such as cracked.Therefore both are all gradually by the thermosetting resin of a new generation---Bulk Molding Compound substitute, this is a kind of primarily of unsaturated polyester resin, filler and short glass fiber and the prepreg of various additive through fully mixing.
But, in order to ensure that its this key index of products formed physical strength meets the high standard of breaker of plastic casing material, the short glass fiber that the moulding compound of unsaturated polyester resin base just must add fiber longer in a large number strengthens, but along with the increase of content of glass fiber and the raising of length, mineral filler and glass fibre itself will inevitably be tending towards deterioration by the effect that resin infiltrates, the overall viscosity of additional material is lower, moulding compound is made very easily to occur the tendency of Solid-Liquid Separation when heating pressurized flow, the solid phase be separated wraps owing to lacking resin, shaping complete time will show as the white piebald of a lot of different sizes, be distributed in the surface of products formed in a jumble, especially comparatively intensive and especially obvious in the position that wall thickness is thinner.For this reason, lot of domestic and foreign enterprises unit and academic institution have carried out large quantity research with regard to this problem and have achieved suitable achievement.
Patent US4263198 discloses a kind of chemical thickening agent being applicable to unsaturated polyester resin based composites, and its concrete composition is the alkalimetal oxide of II A race in the periodic table of elements.The application of this kind of chemical thickening agent has now become the more classical solution of industry, system thickening is carried out as added magnesium oxide in the unsaturated polyester resin of Bulk Molding Compound in advance, improve mixture system viscosity before curing by entirety, what occur when alleviating its processing flowing to a certain extent is separated.But the regulation and control of thickening itself are the complicated technologies of a set of high cost, specifically there are following three broad aspect problems:
1, the quality control aspect of unsaturated polyester resin: the number-average molecular weight of unsaturated polyester resin and acid value, all can have a strong impact on the viscosity upcurve in thickening, finally has influence on the average viscosity of resin and even Bulk Molding Compound.And the manufacturer of a lot of production Bulk Molding Compound itself does not produce resin, therefore do not possess corresponding detection means and specification index is controlled.
2, the use of thickening material: the alkalimetal oxide easy moisture absorption mostly used as thickening material, and thickening has extremely strict requirement for the moisture in system, as when using magnesium oxide 0.1% ~ 0.8% minor amount of water thickening can be made to accelerate, but thickening effectiveness is also poorer than anhydrous on the contrary during more than 1%, thickening failure, resin may be caused residual sticky and material is touched with one's hand more than 1.5%.Therefore some manufacturers can by alkalimetal oxide and inactive resin carrier used in combination to reduce its water absorbability, but this method significantly can improve the finely dispersed difficulty of thickening material, it is homogeneous that the thickening material of pasty state needs extra high-speed stirring premix to carry out guarantee system, this is a kind of common resin container and the inefficient mixing process of kneader, extra equipment must be added complete, and spend extra manpower to manage.
3, the process management and control aspect of later stage slaking: in the various factors affecting resin thickening, temperature is most important factor---too lowly can not reach thickening effectiveness; Too high, seriously can reduce the final mobility of Bulk Molding Compound and processibility.Conventional alkalimetal oxide thickening unsaturated polyester resin moulding compound, the envrionment temperature of 30 ~ 50 DEG C is needed to carry out post curing, short hairs a few hours, length then reach a couple of days, at least more than the several times of mixing process used time, in actual volume production, just need additionally to build drying room realized, not only can take considerable man power and material, also can significantly extend manufacture cycle.
Carry out except ligand complex thickening except being used alone alkalimetal oxide, in " TDI thickening modification SMC studies " of " About Frp/cm " the 2nd phase in 2012 and " the MDI modification BMC research " of phase in the same year the 3rd, researchist is had to propose a kind of alkalimetal oxide in conjunction with tolylene diisocyanate (TDI), the binary isocyanate compounds such as diphenylmethanediisocyanate (MDI) carry out the new approaches of the netted thickening of IPN, although compare traditional basic metal system thickening, this thickening process can improve use properties and the storage life of Bulk Molding Compound to a certain extent, but still this operation the most consuming time of later stage slaking can not be saved.And the price of binary isocyanate compound is higher relative to other raw material in Bulk Molding Compound, comes into operation and can aggravate Cost Problems further in actual volume production.
In addition, patent CN200410013422.9 discloses a kind of low pressure SMC thickening material and preparation method thereof, and in patent CN200510019581.4, propose the technical scheme being applied to produce.According to the technique that above-mentioned patent describes, although effectively reduce the temperature and time requirement of material later stage slaking, but crystallinity unsaturated polyester resin needs the consumption being equivalent to resin total mass mark 20% when being used alone, the sheet molding compound viscosity obtained thus is very high, mobility and processibility limited, products formed is mostly the simple sheet material of structure, cannot tackle the goods that design is complicated.In addition, to temperature control in material when core process in this thickening is rolling, various raw material before combination after temperature variation larger, be difficult to realize in large-scale kneader, then must again add post curing engineering to complete thickening, therefore this thickened systems is not yet applied in traditional Bulk Molding Compound manufacturing process.
Summary of the invention
The object of the invention is: the problem very easily occurring Solid-Liquid Separation for solving moulding compound when heating pressurized flow, and the unsaturated polyester ester composition and Bulk Molding Compound and preparation method thereof of the thickening of a kind of non-alkali metal system are provided.Also solve the series of problems such as the production management cost that traditional Bulk Molding Compound adopts the thickening of basic metal system to bring is high, the production cycle long, quality management and control is numerous and diverse simultaneously.
Know-why of the present invention is: by being mixed into a small amount of modified unsaturated polyester resin in traditional unsaturated polyester resin system, plays the physics thickening effectiveness being different from subsalt and carboxyl coordination complexing.Due to synthesize this modified unsaturated polyester resin raw material in containing the terephthalic acid of more high symmetrical structure, in main chain, form terephthalic acid ester structure after polymerization.The benzene radicals of this structure is connected with the carbonyl of two contrapositions each other, while the rigidity effectively improving linear polymer backbone, by electron conjugated interaction general between molecule segment, making this modified resin compare general unsaturated polyester resin has better normal temperature crystallinity.But the synthesis of this modified unsaturated polyester resin, has strict demand to the consumption of phthalic acid in raw material, and namely its mole fraction should account for 30 ~ 80% of polyprotonic acid mole summation.When consumption is too high, the degree of crystallinity of gained modified unsaturated polyester resin is too high, is difficult in the composition of unsaturated polyester resin dispersed; And when consumption is too low, the structural symmetry of gained modified unsaturated polyester resin and crystallinity can not satisfy the demands, follow-up thickening cannot produce a desired effect.
In temperature-fall period after Bulk Molding Compound is mixing, under the effect of vinylbenzene isoreactivity solvent, the modified resin of uniformly dispersing in system occurs swelling while exothermic crystallization, and a part of vinylbenzene is consumed, and system viscosity rises; The modified resin again becoming crystal grain can become again nucleus and induce other common unsaturated polyester resin crystallization, makes system viscosity increase further, serves the thickening power not second to ligand complex.
In addition, mineral filler granularity that we are also preferred, adopt the combination that median size is little, size distribution is wide, make fine particle to embed medium grain, medium grain embeds big particle then, forms more fine and close micro-arrangement structure, in conjunction with the physics thickening effectiveness of above-mentioned modified unsaturated polyester resin, improve the ability of moving phase entirety conveying stationary phase, to this reduce the consumption of modified unsaturated polyester resin, suitable raw materials cost can be saved.
According to above-mentioned formulating of recipe gained resin and inorganic filler composition, the Bulk Molding Compound made after adding chopped glass fiber and other interpolation auxiliary agent, longer phase steady time can be kept when cryopreservation and the flowing of middle temperature, improve the material homogeneity adding products formed in man-hour, can effectively improve easily appear at goods thin-walled, the problem of appearance that is representative with white piebald.Namely its advantage is not need the viscosity controller operation such as premix post curing before strict management and control, compares the production cycle that traditional basic metal system thickening process significantly reduces material.The present invention is achieved by the following technical solutions:
The unsaturated polyester resin compositions of the non-alkali metal system thickening in the present invention, the unsaturated polyester resin kind for its main part is not particularly limited.As long as the formed material general purpose polyester be made up of unsaturated polyprotonic acid, saturated polybasic acid and polyhydric alcohol, just can adopt.Consider Working environment during actual use, main body can adopt one or more combinations in metaphenylene unsaturated polyester, adjacent benzene-type unsaturated polyester, halo unsaturated polyester, vinyl ester resin.
Wherein, metaphenylene unsaturated polyester have employed m-phthalic acid as saturated polybasic acid, has good mechanical property after shaping; Adjacent benzene-type unsaturated polyester have employed phthalic acid as saturated polybasic acid, and advantage of lower cost is widely used; Halo unsaturated polyester adopts halo saturated acid as saturated polybasic acid, effectively can promote the flame retardant rating of goods; Vinyl ester resin is then synthesized by epoxy resin and unsaturated monoprotic acid, after introducing the modified feedstocks such as dihydroxyphenyl propane, can give the good toughness of goods, thermotolerance and erosion resistance.
Commonly use in unsaturated polyester resin in above-mentioned Bulk Molding Compound, vinyl ester resin can one-step synthesis owing to not having water to generate in building-up process; And metaphenylene, adjacent benzene-type, halo unsaturated polyester most employing two step reaction method produce: cool system to a certain extent afterwards at the first step saturated polybasic acid and polyol reaction, then add unsaturated polyprotonic acid start second step reaction.Two kinds of method gained resins all can retain the active end carboxyl of higher concentration in polyester molecule end, functional group can with basic metal (hydrogen) oxide compound, generates subsalt as magnesium oxide react by this, and then formation co-ordination complex raising system viscosity.In other words, this class unsaturated polyester resin mostly has stable good change thickening properties.But on the other hand, because such unsaturated polyester resin does not pay close attention to the molten limit of resin, crystallinity and structural symmetry in process of production, if do not use alkalimetal oxide system to heat-treat, system viscosity does not have obvious change for a long time, namely effective thickening does not occur.Will there is Solid-Liquid Separation when heating pressurized flow in Bulk Molding Compound obtained thus, the problem such as bad order, undercapacity easily appears in products formed.
Modified unsaturated polyester resin in of the present invention, is formed by polyvalent alcohol and polyprotonic acid condensation polymerization, and wherein the mole fraction of terephthalic acid accounts for 30 ~ 80% of polyprotonic acid mole summation, also adopts two step reaction method preparations.Pay close attention to the normal temperature crystallinity after resins synthesis, adopt terephthalic acid that symmetrical configuration degree is higher as saturated polybasic acid.Consider physical strength and the formability of goods, unsaturated polyprotonic acid adopts maleic anhydride; Polyvalent alcohol then adopts neopentyl glycol and the ethylene glycol of high symmetrical structure.The mol ratio of terephthalic acid, maleic anhydride, ethylene glycol and neopentyl glycol is designed to as 3:2:5:5, get massfraction be the organotin of 0.2% as catalyzer, retarder functional quality mark is the quinhydrones of 0.02%.First ethylene glycol, neopentyl glycol and terephthalic acid are added reaction vessel, pass into nitrogen simultaneously and be heated to 85 DEG C, stirring heating is started after alcohol acid dissolve, with 1.5 hours progressively heating systems to 160 DEG C (system thermopositive reaction can occur in heat-processed, now notes computer heating control).When system reaches 160 degrees Celsius, slowly heated up 15 DEG C with 1 hour and be incubated 1 hour again, heating and heat preservation is carried out repeatedly.Start to dewater when temperature reaches 190.System temperature is risen to 220 DEG C by the circulation until after temperature reaches 205 DEG C, control viscosity by detection system acid value, when acid value is cooled to 160 DEG C lower than during 15mg KOH/g, added by maleic anhydride and participate in reaction, to use equally liter, being incubated each 1 hour.Again detect acid value, when acid value is cooled to 160 DEG C lower than during 25mg KOH/g, add quinhydrones stopped reaction, after system naturally cooling, namely discharging obtains modified unsaturated polyester resin required in subsequent embodiment.
In the present invention, the consumption of modified unsaturated polyester resin should account for 5 ~ 15% of unsaturated polyester resin compositions total mass mark, consider the processibility of Bulk Molding Compound, products appearance and various use properties, the massfraction of unsaturated polyester resin compositions should control in the scope of Bulk Molding Compound total mass mark 15 ~ 30%.
Bulk Molding Compound involved in the present invention, except comprising above-mentioned unsaturated polyester resin compositions, all the other components comprise inorganic filler composition, linking agent, initiator, retarder, shrinking agent, internal mold release and short glass fiber and are mixed in proportion and make.
Inorganic filler composition in the present invention, main body is two or more combinations of the aluminium hydroxide of different-grain diameter or the calcium carbonate of different-grain diameter.Consider that target product has flame retardant rating requirement as electric correlated parts, subsequent embodiment all using aluminium hydroxide as mineral filler main body, control its massfraction inorganic filler composition total mass mark more than 80%.And in order to coordinate the thickening effectiveness of above-mentioned modified resin, strict demand is had: the combination that median size is little, size distribution is wide must be adopted to the grain size specification of mineral filler main body, guarantee that filler fine particle can embed medium grain, medium grain embeds big particle then, forms fine and close micro-arrangement structure.The packing material size of all kinds should control in the scope of 1 ~ 40 μm, and the grain size distribution curve of single filler has obviously bimodal, and two kinds of mineral filler median size D that particle diameter is close
50difference be 6 ~ 10 μm.Packing material size is too small, the oil absorbency entirety of inorganic system can be caused to improve, for ensureing that the forming process sexual needs of Bulk Molding Compound significantly increase consumption and even the material cost of unsaturated polyester.And packing material size and difference excessive, then cannot form the micro-arrangement structure of above-mentioned densification, the thickening effectiveness of above-mentioned modified resin can be caused obviously to reduce.Add the consideration of the problems such as the processibility to Bulk Molding Compound, products appearance and various use propertieies, the massfraction of inorganic filler composition is preferably in the scope of Bulk Molding Compound total mass mark 40 ~ 60%.Wherein the concrete composition of all the other components of mineral filler can require according to the physical property of goods and the actual shaping characteristic of mould, and one or more can selecting in glass powder, glass hollow microballon, quartz sand, china clay, talcum powder, calcium sulfate, silicon-dioxide combine.
Linking agent in the present invention is free-radical polymerised unsaturated monomer, effect is that bridge joint unsaturated polyester resin main chain makes it solidification in moulding process, also can produce certain diluting effect to shaping front resin simultaneously, and small molecule monomer volatile can improve Bulk Molding Compound shaping before inflammableness, therefore used in amounts is moderate.Specifically can adopt one or more combinations in vinylbenzene, diallyl phthalate ester and methyl methacrylate.From guaranteeing forming materials, shrink of product rate and raw materials cost angularly, the linking agent in subsequent embodiment all uses vinylbenzene, and its massfraction is 1 ~ 4% of Bulk Molding Compound total mass mark.
In the present invention, initiator is organo-peroxide, specifically can adopt one or more combinations in peroxidized t-butyl perbenzoate, the peroxidation isocaprylic acid tert-butyl ester, dibenzoyl peroxide, dicumyl peroxide.The key distinction between these initiators is active o content, decomposition temperature and transformation period.Consider actual mold temperature and the degree of cure requirement of target product, all adopt peroxidized t-butyl perbenzoate and the peroxidation isocaprylic acid tert-butyl ester as middle temperature initiator system in subsequent embodiment, its massfraction is 0.3 ~ 0.6% of Bulk Molding Compound total mass mark.
Retarder main body in the present invention adopts and combines one or more in biphenol biphenol, the tertiary butyl biphenol, para benzoquinone, methyl.Wherein the mechanism of action of phenols retarder is for guiding free radical generation chain transfer reaction; Benzoquinones class retarder is then by reaching with free radical generation addition reaction the object controlling reaction process.Consider the dispersiveness in system of solid-state retarder, the keeping quality of Bulk Molding Compound, and the temperature, pressure of target product in actual moulding process and production cycle need, all adopt massfraction to be 5% para benzoquinone-methyl methacrylate solution in embodiment, the consumption of this retarder solution is 0.1 ~ 0.3% of Bulk Molding Compound total mass mark.
Shrinking agent in the present invention adopts one or more combinations in polymethyl methacrylate copolymer, polyvinyl acetate copolymer, nylon, saturated polyester, homopolystyrene crystal grain, polyethylene micropowder, styrene-butadiene rubber(SBR) pulverizing product.Because excessive shrinking agent can extend the set time of resin system, exothermic peak temperature is caused to reduce, namely suitable plastification is created to the cross-linked network of thermosetting resin, not only can reduce degree of cure and the intensity of resin system, and Bulk Molding Compound obtained thus can be hardened, processibility is deteriorated; And shrinking agent consumption crosses the effect that can not play at least and reduce and shrink trace, ripple and profile.Consider outward appearance and the intensity needs of target product, subsequent embodiment is preferred, and homopolystyrene crystal grain, polyethylene micropowder and styrene-butadiene rubber(SBR) pulverize the lower shrinkage system that product press the combination of 4:2:3 mass ratio, and its massfraction is 2 ~ 5% of Bulk Molding Compound total mass mark.
Internal mold release in the present invention adopts one or more combinations in stearic acid, Zinic stearas, calcium stearate, aluminum stearate, Magnesium Stearate.Above-mentioned stearic acid and salt, after adding unsaturated polyester resin system, melting can migrate to product surface formation sealing coat when shaping, make originally have the vibrin of polarity and the contact surface of metal die to reduce, can reduce the consumption of spary coating type external release agent.But too much inner pattern releasing agent applicable should not be uniformly dispersed, highly enriched meeting forms hickie at product surface and causes bad order.Based on above-mentioned consideration, the inner pattern releasing agent applicable in subsequent embodiment all adopts Zinic stearas micro mist, and its massfraction is 1 ~ 3% of Bulk Molding Compound total mass mark.
Short glass fiber in the present invention does not have particular requirement as strongthener main body, as long as through surface treatment, can the kind that is dispersed in unsaturated polyester resin system of homogeneous immersion can adopt.Length can be adopted to be one or more combinations in 1.5mm, 3mm, 6mm, 9mm, 12mm, 24mm according to the actual size of actual product and requirement of strength.Because target product of the present invention there are certain requirements intensity, and pressing structure is comparatively simple and easy, therefore the short glass fiber in subsequent embodiment all adopts length to be the specification of 6mm and 12mm, combine by the mass ratio of 1:4, its massfraction is 15 ~ 30% of Bulk Molding Compound total mass mark.
In the present invention the producing apparatus of Bulk Molding Compound and flow process simple and easy, with short production cycle, concrete main points are as follows:
A) the two wrist-kneader Homogeneous phase mixing of omnidistance employing, the rotating ratio of two blades is 5:4, and wherein fast oar is 30r/min;
By in disposable to unsaturated polyester resin compositions, linking agent, initiator, retarder, shrinking agent, mineral filler and internal mold release whole input kneader, refine 30 minutes in controlled circulation water temperature 60 DEG C;
B) add short glass fiber again, controlled circulation water temperature 60 DEG C mixing 8 minutes, after be cooled to room temperature discharging, obtain Bulk Molding Compound of the present invention.
Advantage of the present invention is:
The unsaturated polyester ester composition and Bulk Molding Compound and preparation method thereof of a kind of non-alkali metal system provided by the invention thickening, solve Solid-Liquid Separation very easily appears in moulding compound problem when heating pressurized flow well.
Owing to not adopting traditional basic metal system to carry out thickening, therefore without the need to viscosity controller operations such as premix post curings before extra, expensive viscosity-depression agent and treating compound also need not be added, and omnidistance employing kneader mixing, the energy consumption of production unit can be saved.Bulk Molding Compound involved in the present invention can adopt mold pressing, transfer, injection three kinds of moulding processs, and the equal product that obtained products formed compares the thickening of basic metal system have better thin-walled outward appearance and physical strength.
Also solve the series of problems such as the production management cost that traditional Bulk Molding Compound adopts the thickening of basic metal system to bring is high, the production cycle long, quality management and control is numerous and diverse simultaneously.
Accompanying drawing explanation
Fig. 1 is embodiments of the invention effect view
Fig. 2 is comparative example effect view
Specific embodiment
Below will be illustrated feature of the present invention by embodiment and comparative example, but not be the restriction to invention itself.
To the primary evaluation project of Bulk Molding Compound in embodiment and comparative example and testing method as follows:
1. thin plate outward appearance:
63 tons of compression molding forming machines, under the mold temperature of 140 DEG C, use maximum output the material in embodiment to be compressed to the thin plate (central ejector rod place is 0.5mm) of 320mm × 220mm × 1mm, evaluate thin plate outward appearance.Evaluation result marks with "excellent", "fine", "moderate" and "bad", and specific standards boundary is see accompanying drawing, and wherein Fig. 1 is excellent, is specially the effect view of embodiment 3 in the present invention;
Fig. 2, for poor, is specially the effect view of comparative example 1.
The main purpose of this project is the thickening effectiveness of evaluation and test Bulk Molding Compound: because the system viscosity of the bad Bulk Molding Compound of thickening is lower, it is made very easily to occur the tendency of Solid-Liquid Separation when heating pressurized flow, the solid phase be separated wraps owing to lacking resin, shaping complete time will show as the white piebald of a lot of different sizes.
2. flexural strength:
Specify that production standard bends batten and measuring and calculation according in JIS K 6911-5.17, effective sample number is 5.
3. simple beam impact strength:
According to specifying in JIS K 6911-5.20 that production standard impacts sample block and measuring and calculation, effective sample number is 5.
The test result of above-mentioned assessment item is as shown in Table 1:
Table one
Above technical scheme and embodiment are the concrete elaboration to the principle of the invention and implementation method, not departing from the improvement and derivative coordinator and method that occur under the prerequisite of technical solution of the present invention, all in the protection domain of claim of the present invention.
Claims (10)
1. a unsaturated polyester resin compositions for non-alkali metal system thickening, is characterized in that:
(1) main body is one or more combinations in metaphenylene unsaturated polyester, adjacent benzene-type unsaturated polyester, halo unsaturated polyester, vinyl ester resin;
(2) containing the modified unsaturated polyester resin accounting for unsaturated polyester resin compositions total mass mark 5 ~ 15%, be formed by polyvalent alcohol and polyprotonic acid condensation polymerization, wherein the mole fraction of terephthalic acid accounts for 30 ~ 80% of polyprotonic acid mole summation.
2. comprise a Bulk Molding Compound for unsaturated polyester resin compositions according to claim 1, all the other components of Bulk Molding Compound are that inorganic filler composition, linking agent, initiator, retarder, shrinking agent, internal mold release and short glass fiber are mixed in proportion composition.
3. Bulk Molding Compound as claimed in claim 2, is characterized in that the massfraction of unsaturated polyester resin compositions as claimed in claim 1 accounts for 15 ~ 30% of Bulk Molding Compound total mass mark.
4. Bulk Molding Compound as claimed in claim 2, wherein inorganic filler composition is characterised in that:
(1) main body is two or more combinations of the aluminium hydroxide of different-grain diameter or the calcium carbonate of different-grain diameter, preferable particle size scope 1 ~ 40 μm, and the grain size distribution curve of single filler has obviously bimodal, and two kinds of mineral filler median size D that particle diameter is close
50difference be 6 ~ 10 μm, the massfraction of main body controls at more than 80% of inorganic filler composition total mass mark;
(2) all the other components are one or more combinations in glass powder, glass hollow microballon, quartz sand, china clay, talcum powder, calcium sulfate, silicon-dioxide;
(3) massfraction of inorganic filler composition accounts for 40 ~ 60% of Bulk Molding Compound total mass mark.
5. Bulk Molding Compound as claimed in claim 2, linking agent is one or more combinations in vinylbenzene, diallyl phthalate ester and methyl methacrylate, and its massfraction accounts for 1 ~ 4% of Bulk Molding Compound total mass mark.
6. Bulk Molding Compound as claimed in claim 2, initiator is one or more combinations in peroxidized t-butyl perbenzoate, the peroxidation isocaprylic acid tert-butyl ester, dibenzoyl peroxide, dicumyl peroxide, and its massfraction accounts for 0.3 ~ 0.6% of Bulk Molding Compound total mass mark.
7. Bulk Molding Compound as claimed in claim 2, the main body of retarder is combine one or more in biphenol biphenol, the tertiary butyl biphenol, para benzoquinone, methyl, dissolve in obtained solution after methyl methacrylate, retarder solution usage accounts for 0.1 ~ 0.3% of Bulk Molding Compound total mass mark.
8. Bulk Molding Compound as claimed in claim 2, shrinking agent is one or more combinations in polymethyl methacrylate copolymer, polyvinyl acetate copolymer, nylon, saturated polyester, homopolystyrene crystal grain, polyethylene micropowder, styrene-butadiene rubber(SBR) pulverizing product, and its massfraction accounts for 2 ~ 5% of Bulk Molding Compound total mass mark.
9. Bulk Molding Compound as claimed in claim 2, internal mold release is one or more combinations in stearic acid, Zinic stearas, calcium stearate, aluminum stearate, Magnesium Stearate, and its massfraction accounts for 1 ~ 3% of Bulk Molding Compound total mass mark.
10. Bulk Molding Compound as claimed in claim 2, the length of short glass fiber is one or more combinations in 1.5mm, 3mm, 6mm, 9mm, 12mm, 24mm, and its massfraction accounts for 15 ~ 30% of Bulk Molding Compound total mass mark.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0536629A2 (en) * | 1991-10-11 | 1993-04-14 | BASF Aktiengesellschaft | Curable polyester molding compositions having low shrinkage |
| CN1594432A (en) * | 2004-07-06 | 2005-03-16 | 武汉理工大学 | Low-pressure SMC thickening agent and method for preparing same |
| CN1760267A (en) * | 2005-10-13 | 2006-04-19 | 武汉理工大学 | Technique and equipment for fabricating plastic sheet material produced from molding laminar die in low pressure |
| US20070249774A1 (en) * | 2002-06-28 | 2007-10-25 | Robert Guzauskas | Molding compositions with solid thermoplastic elastomer thickeners and products obtained therefrom |
| CN102643524A (en) * | 2012-04-24 | 2012-08-22 | 上海昭和高分子有限公司 | Unsaturated polyester bulk molding compound as well as method and application thereof |
-
2014
- 2014-12-05 CN CN201410739970.3A patent/CN104371237B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0536629A2 (en) * | 1991-10-11 | 1993-04-14 | BASF Aktiengesellschaft | Curable polyester molding compositions having low shrinkage |
| US20070249774A1 (en) * | 2002-06-28 | 2007-10-25 | Robert Guzauskas | Molding compositions with solid thermoplastic elastomer thickeners and products obtained therefrom |
| CN1594432A (en) * | 2004-07-06 | 2005-03-16 | 武汉理工大学 | Low-pressure SMC thickening agent and method for preparing same |
| CN1760267A (en) * | 2005-10-13 | 2006-04-19 | 武汉理工大学 | Technique and equipment for fabricating plastic sheet material produced from molding laminar die in low pressure |
| CN102643524A (en) * | 2012-04-24 | 2012-08-22 | 上海昭和高分子有限公司 | Unsaturated polyester bulk molding compound as well as method and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| 上海化工学院玻璃教研室: "《合成树脂》", 31 December 1979 * |
| 李建 等: "低压片状模塑料中结晶树脂的增稠机理探讨", 《高分子材料科学与工程》 * |
| 沃丁柱: "《复合材料大全》", 31 January 2000 * |
| 陈锋: "《BMC模塑料及其成型技术》", 31 August 2003 * |
| 黄家康: "《聚酯模塑料生产与成型技术》", 31 August 2002 * |
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| CN111201280A (en) * | 2017-12-11 | 2020-05-26 | 昭和电工株式会社 | Unsaturated polyester resin composition, molded article containing cured product thereof, and lamp reflector containing the molded article |
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