CN102311523A - Unsaturated polyester resin for vacuum infusion process and resin composition thereof - Google Patents
Unsaturated polyester resin for vacuum infusion process and resin composition thereof Download PDFInfo
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Abstract
The invention discloses an unsaturated polyester resin for a vacuum infusion process. Monomers such as propylene glycol, ethylene glycol, m-phthalic acid, maleic anhydride and the like are prepared into unsaturated polyester through condensation polymerization reaction, then the unsaturated polyester is added into styrene to prepare the unsaturated polyester resin and the unsaturated polyester resin is matched with auxiliary agents such as an H-90 exothermic peak inhibitor, diethylbenzene, copper uversol and the like to form a composition. In the invention, the m-phthalic acid is used as a saturated acid to be introduced into the resin, so that the heat resistance and the corrosion resistance of the resin are improved; the auxiliary agents such as the H-90 exothermic peak inhibitor, the copper uversol and the like are adopted, so that the poor phenomena such as product crack, local burning and the like caused by over-high heat release during resin solidification are effectively avoided; and the diethylbenzene is adopted, so that the demolding strength of a product can be achieved in 3-5 hours. The technical scheme provided by the invention is suitable for large-sized glass fiber reinforced plastic produced by the vacuum infusion process, in particular to large-sized thick workpieces, the glass fiber reinforced plastic products, such as fan housings, glass fiber reinforced plastic boats and the like, and the strength, the weather resistance and the water resistance of the product are improved.
Description
Technical field
The present invention relates to a kind of unsaturated polyester resin, relate in particular to a kind of unsaturated polyester resin that is used for the vacuum introducing technology, this resin is applicable to the goods of producing the large glass steelwork with the vacuum introducing technology with the resin combination that obtains after auxiliary agent mixes mutually.
Background technology
Glass reinforced plastic (Fiber Reinforced Plastic; FRP) be as strongthener with spun glass and goods (woven fiber glass, band, felt and yarn etc.) thereof; Make a kind of matrix material of body material with synthetic resins; Be also referred to as glass filament reinforced plastics, mainly have following characteristics: 1. light weight is high-strength, and tensile strength is 4 times-6 times of ordinary steel.2. corrosion-resistant, anti-aging, be work-ing life 50 years.3. easy-formation, designability are strong.4. good insulation performance property and thermotolerance are arranged.
Chinese invention patent ZL85108789 discloses a kind of fiber size for reinforcemeent that is used for reinforced plastic glass fibre, is made up of coupling agent, membrane-forming agent, lubricant, softening agent, tensio-active agent and static inhibitor.Treating compound and matrix resin, spun glass have close specific refractory power; Improve the transmittance of glass reinforced plastic; The contact area of matrix resin and spun glass in the increase glass reinforced plastic; Make the perfect condition that consists of resin-coupling agent-spun glass of boundary material, thereby improved the water tolerance and the weather resisteant of glass reinforced plastic.Treating compound is the unsaturated polyester resin as the glass reinforced plastic matrix resin.
Chinese invention patent ZL200610025003.6 discloses a kind of method of producing terephthalic unsaturated polyester resin with the terephthalic acid rinsing residue; To contain terephthalic acid 80%-90%; The terephthalic acid rinsing residue of p-methylbenzoic acid 10%-20% is produced terephthalic unsaturated polyester resin as raw material.This method is included in the terephthalic acid rinsing residue and adds divalent alcohol and carry out the esterifying polycondensation reaction with composite catalyst, adds unsaturated dibasic acid again and further carries out esterifying polycondensation and react, and carries out crosslinking reaction with vinylbenzene at last.In the terephthalic acid rinsing residue, can sneak into the moisture of 0%-40%, terephthalic acid all replaces phthalic anhydride and diol reaction in the terephthalic acid rinsing residue, and p-methylbenzoic acid is participated in reaction mainly as the end-block agent.The terephthalic unsaturated polyester resin that makes can be widely used in GRP pipe, storage tank or the equipment lining of various acid-and base-resisting, salt and organic solvent.
Along with the continuous development and the extension of glass reinforced plastic industry, large glass steel work such as glass reinforced plastic ships and light boats and wind-power electricity generation cabin cover has also obtained to develop flourishingly in recent years, and especially the wind-powered electricity generation industry has become the hot topic of glass reinforced plastic industry at present.Meanwhile, market and user also have higher requirement with the quality of unsaturated polyester resin to glass reinforced plastic.But conventional glass steel resin can only be fit to the glass fiber reinforced plastics product of manufacturing small-sized owing to shortcomings such as heat release peak height, poor toughness; On the other hand, the product size precision made of traditional hand technology is poor, production efficiency is low and problem such as work under bad environment.
Chinese invention patent application 200910012662.X discloses a kind of low volatilization of large glass steelwork layer usefulness unsaturated polyester resin that is used to make, and it is dissolved in a kind of unsaturated polyester resin formulated in the vinylbenzene again by Ucar 35, terepthaloyl moietie, hexanodioic acid, phthalic anhydride, MALEIC ANHYDRIDE after condensation.In unsaturated polyester resin, add N20 type aerosil, M30 exothermic peak suppressor factor and 0.02 part of B20 tensio-active agent; The thixotropy index and the viscosity that evenly reach specified requirement through the stirrer high speed dispersion are promptly applicable to the large-scale thick product glass fiber reinforced plastics product of sag preventions such as fan shroud, glass reinforced plastic ships and light boats, and the goods that make have characteristics such as intensity height, good weatherability and water-tolerant.
The vacuum introducing technology is the wider glass reinforced plastic production technique of current application, and at present, domestic still do not have a kind of metaphenylene unsaturated polyester resin can in this technology, be applicable to production glass fiber reinforced plastics product, especially large-scale glass fibre reinforced plastic products.
Summary of the invention
One object of the present invention is to provide a kind of unsaturated polyester resin that is used for the vacuum introducing technology, effectively solves the vacuum introducing technology and produces the problem that lacks suitable matrix resin in glass fibre reinforced plastic structure goods, especially the large glass steelwork goods.
Another object of the present invention is to provide a kind of unsaturated polyester resin compositions that is used for the vacuum introducing technology; Effectively solve the vacuum introducing technology and produce the problem that lacks suitable matrix resin in glass fibre reinforced plastic structure goods, especially the large glass steelwork goods.
Unsaturated polyester resin provided by the invention comprises Ucar 35, terepthaloyl moietie, m-phthalic acid, MALEIC ANHYDRIDE and vinylbenzene.
Ucar 35 is a kind of divalent alcohol, easy and diprotic acid generation esterification, and it can give characteristics such as resin physical strength height and water-tolerant.This compound has following physicochemical characteristic:
Molecular weight: 76.09.
Outward appearance: water white transparency or faint yellow liquid with peculiar taste.
Boiling range: 184-190 ℃.
Refractive index (25 ℃): 1.431-1.435.
Density (20 ℃, g/cm
3): 1.037-1.039.
Solvability: miscible with the water arbitrary proportion.
In the unsaturated polyester resin provided by the invention, the shared weight part of Ucar 35 is 100-130 part, preferentially selects 105-120 part, further selects 110 parts.
Terepthaloyl moietie is a kind of divalent alcohol, easy and diprotic acid generation esterification, and it can give characteristics such as resin physical strength height and water-tolerant.This compound has following physicochemical characteristic:
Molecular weight: 62.07.
Outward appearance: colourless transparent liquid.
Boiling range: 196-199 ℃.
Refractive index (25 ℃): 1.4300-1.4330.
Density (20 ℃, g/cm
3): 1.1128-1.1138.
Solvability: miscible with the water arbitrary proportion.
In the unsaturated polyester resin provided by the invention, the shared weight part of terepthaloyl moietie is 3-7 part, preferentially selects 4-6 part, further selects 5 parts.
M-phthalic acid is a kind of monounsaturated dicarboxylic acid; Under catalyzer (as: Mono-n-butyltin) effect; Easily, partly replace the degree of unsaturation of MALEIC ANHYDRIDE adjustable unsaturated polyester, give resin excellent mechanical property, water tolerance and thermotolerance with divalent alcohol generation esterification.This compound has following physicochemical characteristic:
Molecular weight: 166.13.
Outward appearance: crystalline powder.
Fusing point: 345-348 ℃.
Specific density: 1.507.
Solvability: be soluble in ethanol.
In the unsaturated polyester resin provided by the invention, the shared weight part of m-phthalic acid is 100-120 part, preferentially selects 105-110 part, more preferably selects 105 parts.
MALEIC ANHYDRIDE, easy and divalent alcohol generation esterification provides the unsaturated double-bond in the unsaturated polyester, can give the resin excellent mechanical property.This compound has following physicochemical characteristic:
Molecular weight: 98.06.
Outward appearance: white, little yellow bulk or crystalline powder.
Fusing point: 52.8 ℃.
Boiling point: 202.2 ℃.
Specific density: 1.48.
Solvability: water soluble is slightly soluble in alcohol.
In the unsaturated polyester resin provided by the invention, the shared weight part of MALEIC ANHYDRIDE is 60-80 part, preferentially selects 65-76 part, more preferably selects 70 parts.
Vinylbenzene is the thinner of unsaturated polyester, and the two keys on the vinylbenzene in the vinyl can be used for the crosslinked of vibrin, makes resin solidification and shows excellent mechanical property.This compound has following physicochemical characteristic:
Molecular weight: 104.15.
Outward appearance: colourless transparent liquid.
Specific density: 0.9.
Vp (25 ℃): 880Pa.
Refractive index (25 ℃): 1.5436.
Solvability: can be dissolved in alcohol, ether in all proportions, be slightly soluble in water.
In the unsaturated polyester resin provided by the invention, the shared weight part of vinylbenzene is 160-200 part, preferentially selects 170-190 part, more preferably selects 180 parts.
A kind of unsaturated polyester resin provided by the invention comprises following components by part by weight: Ucar 35 100-130 part, terepthaloyl moietie 3-7 part, m-phthalic acid 100-120 part, MALEIC ANHYDRIDE 60-80 part and vinylbenzene 160-200 part.
Another kind of unsaturated polyester resin provided by the invention comprises following components by part by weight: Ucar 35 105-120 part, terepthaloyl moietie 4-6 part, m-phthalic acid 105-110 part, MALEIC ANHYDRIDE 65-76 part and vinylbenzene 170-190 part.
Another kind of unsaturated polyester resin provided by the invention comprises following components by part by weight: 180 parts of 110 parts of Ucar 35,5 parts of terepthaloyl moietie, 105 parts of m-phthalic acids, 70 parts of MALEIC ANHYDRIDEs and vinylbenzene.
Monomers such as Ucar 35, terepthaloyl moietie, m-phthalic acid and MALEIC ANHYDRIDE add the crosslinked unsaturated polyester resin of processing in the vinylbenzene after processing unsaturated polyester through polycondensation again.Those skilled in the art are according to textbook, laboratory manual or the guidance of open source literature; Just can make unsaturated polyester resin of the present invention through polymerization procedure commonly used or method (comprise the consumption of catalyst type is selected), as: drop into Ucar 35, terepthaloyl moietie, m-phthalic acid and catalyzer (as: Mono-n-butyltin) in the reaction kettle successively; Under the nitrogen protection in 200-210 ℃ of polycondensation; When solid acid number 20mgKOH/g is following, be cooled to below 155 ℃, in reaction kettle, add MALEIC ANHYDRIDE, continue to be warming up to 200-210 ℃ of reaction; When the solid acid number is 49-53mgKOH/g, be evacuated to vacuum tightness-80kPa, cone-plate viscosity (No. 3 rotors, 150 ℃) is removed vacuum during for 600-690mPas and is cooled off more than 175 ℃; Add to polyester that reaction obtains and to fill in the cinnamic dilution still, make unsaturated polyester resin after being cooled to 30-40 ℃.
Unsaturated polyester resin includes the hundreds of kind, but the collocation of its employed main raw material and various auxiliary agent, and mutually is that can the decision unsaturated polyester resin be applicable to that the vacuum introducing technology produces the key of large glass steel with magnitude relation.
On the basis of various unsaturated polyester resins provided by the invention, cooperate with one or more auxiliary agents such as H-90 exothermic peak suppressor factor, Diethyl Aniline and copper naphthenates, the unsaturated polyester resin that makes can be applicable to vacuum introducing technology production large glass steel.
H-90 exothermic peak suppressor factor, promptly methyldiphenyl base amylene is a kind of double bond containing organic solvent.Itself and resin intermiscibility are good, are unsaturated polyester resin retarders the most efficiently, through the space steric effect of methyl, can obviously reduce exothermic peak, satisfy the different processes requirement, can prolong the set time in early stage of unsaturated polyester resin.This compound has following physicochemical characteristic:
Outward appearance: colourless to little yellow transparent liquid.
Density (25 ℃ of g/cm3): 0.905-0.915.
Refractive index (20 ℃): 1.56-1.57.
Colourity :≤3.
Solvability: water insoluble, dissolve in pure and mild ether.
In the unsaturated polyester resin provided by the invention, the shared weight part of H-90 exothermic peak suppressor factor is 3-6 part, preferentially selects 4-6 part, more preferably selects 4.7 parts.
Diethyl Aniline has resin solidification exothermic character and the characteristics that shorten the resin solidification time of changing.This compound has following physicochemical characteristic:
Outward appearance: colourless to yellow oily liquid, have special smelly.
Fusing point :-38.8 ℃.
Boiling point: 215 ℃.
Specific density: 0.93
Solvability: water-soluble, be slightly soluble in ethanol, ether.
In the unsaturated polyester resin provided by the invention, the shared weight part of Diethyl Aniline is 0.30-0.80 part, preferentially selects 0.40-0.60 part, more preferably selects 0.45 part.
Copper naphthenate has the vinylbenzene of the preventing solidified effect of being heated, and in unsaturated polyester resin, has the function that resistance gathers and reduce the resin exothermic peak.This compound has following physicochemical characteristic:
Outward appearance: deep green uniform liquid.
Fusing point :-7.2 ℃.
Boiling point: 228 ℃.
Specific density: 0.95.
Solvability: water insoluble, be dissolved in ethanol, ether, toluene, turps and rosin.
In the unsaturated polyester resin provided by the invention, the shared weight part of copper naphthenate is 0.10-0.30 part, preferentially selects 0.20-0.30 part, more preferably selects 0.25 part.
On the basis of various unsaturated polyester resins provided by the invention; Mixing is with a kind of or several kinds of auxiliary agents of H-90 exothermic peak suppressor factor, Diethyl Aniline and copper naphthenate, and the unsaturated polyester resin compositions that evenly makes through the stirrer high speed dispersion can be applicable to vacuum introducing technology production large glass steel.
Another kind of unsaturated polyester resin compositions provided by the invention; Compsn is made up of unsaturated polyester and auxiliary agent, and unsaturated polyester resin is made up of following components by part by weight: Ucar 35 100-130 part, terepthaloyl moietie 3-7 part, m-phthalic acid 100-120 part, MALEIC ANHYDRIDE 60-80 part and vinylbenzene 160-200 part; Auxiliary agent comprises H-90 exothermic peak suppressor factor 3-6 part, Diethyl Aniline 0.3-0.8 part and copper naphthenate 0.10-0.30 part.
Another kind of unsaturated polyester resin compositions provided by the invention; Compsn is made up of unsaturated polyester and auxiliary agent, and unsaturated polyester resin is made up of following components by part by weight: Ucar 35 105-120 part, terepthaloyl moietie 4-6 part, m-phthalic acid 105-110 part, MALEIC ANHYDRIDE 65-76 part and vinylbenzene 170-190 part; Auxiliary agent comprises H-90 exothermic peak inhibitors 4-6 part, Diethyl Aniline 0.40-0.60 part and copper naphthenate 0.20-0.30 part.
Another kind of unsaturated polyester resin compositions provided by the invention; Compsn is made up of unsaturated polyester and auxiliary agent, and unsaturated polyester resin is made up of following components by part by weight: 180 parts of 110 parts of Ucar 35,5 parts of terepthaloyl moietie, 105 parts of m-phthalic acids, 70 parts of MALEIC ANHYDRIDEs and vinylbenzene; Auxiliary agent comprises 0.25 part of H-90 exothermic peak inhibitors 4 .7 part, 0.45 part of Diethyl Aniline and copper naphthenate.
Various unsaturated polyester resin provided by the invention and unsaturated polyester resin compositions are applicable to the goods with vacuum introducing technology or resin transfer molding explained hereafter large glass steelwork.
The beneficial effect that technical scheme of the present invention realizes:
The unsaturated polyester resin that is used for the vacuum introducing technology provided by the invention; Through after polycondensation processes unsaturated polyester, add the crosslinked unsaturated polyester resin of processing in the vinylbenzene by monomers such as Ucar 35, terepthaloyl moietie, m-phthalic acid and MALEIC ANHYDRIDEs again.Adopt m-phthalic acid to introduce in the resin, improved the heat-resisting and corrosion resistance nature of resin as saturated acid.
The unsaturated polyester resin compositions that is used for the vacuum introducing technology provided by the invention; Adopt auxiliary agents such as H-90 exothermic peak suppressor factor and copper naphthenate to make the exothermic peak of resin be controlled at 80-100 ℃; Do not influence the set time of goods, the too high goods cracking that causes of heat release when effectively having avoided, shrink and local generation of bad phenomenon such as burning because of resin solidification.Adopt Diethyl Aniline as promotor, shorten the set time of goods, but guarantee that goods reached the intensity of the demoulding in 3-5 hour.
Unsaturated polyester resin and the compsn thereof that is used for the vacuum introducing technology of the present invention has the satisfactory stability performance, and preparation technology is simple, is easy to operate and control.These compsns are applicable to the large glass steel that the vacuum introducing technology is produced, and are particularly useful for large-scale thick product glass fiber reinforced plastics products such as fan shroud, glass reinforced plastic ships and light boats, improve intensity, weathering resistance and the water tolerance of goods.
Term involved in the present invention is identical with notion as the one of which.
Said " glass reinforced plastic " or " glass fibre reinforced plastic structure " are glass fiber reinforced plastics composite materials, comprise strongthener and the body material that constitutes with synthetic resins.Strongthener wherein also include but not limited to except that spun glass, thomel, boron fibre, aramid fiber, sapphire whisker and silicon carbide fiber etc.
Said " vacuum introducing technology " is called for short VIP (Vacuum infusion process); Be " to do " strongthener (as: spun glass, thomel and/or sandwich material etc.) on the mould upper berth, spread vacuum bag then, and the vacuum in the extraction system; In mold cavity, form a negative pressure; The pressure that utilizes vacuum to produce is pressed into unsaturated polyester in the layer of fibers through the pipeline that overlays and makes resin soak into strongthener, is full of entire die at last, after goods solidify; Throw off vacuum bag material, obtain required goods from mould.
The general step of this technology is following:
The first step: prepare mould, die surface will have higher hardness and higher gloss, and die edge keeps 15 centimetres at least, is convenient to the laying of sealed strip and pipeline.Mould is cleaned out, played demoulding wax then or smear demoulding water;
Second step: construction gel coat face, according to product requirements, can use product gel coat and polishing gel coat, select for use type that adjacent benzene is arranged, a benzene and vinyl.Method construction gel coat with hand brush and injection;
The 3rd step: strongthener is laid, and selects strongthener for use, as: spun glass, thomel or sandwich material etc., also to confirm according to the requirement of strength of goods;
The 4th step: vacuum bag material is laid, and spreads release cloth earlier, then is flow-guiding cloth, is vacuum bag at last.Before the vacuum bag that closes, think over the trend of resin and vacuum-pumping pipeline, so that strongthener can fully be soaked into by resin;
The 5th step: vacuumize, spread these materials after, clamp the entrance of each feeding resin, whole system is vacuumized, find time the system air as far as possible, and check resistance to air loss;
The 6th step: join resin, vacuumize reach certain requirement after, prepare resin.Allocate corresponding curing agent into by gel time;
The 7th step: import resin, insert the pipeline that feeds resin in the resin bucket for preparing, open folder successively according to the charging order;
The 8th step: the demoulding, resin gel are thrown off vacuum bag material after being cured to a certain degree.Take out goods and carry out aftertreatment from mould.
The Application Areas of vacuum introducing technology has: 1) Shipbuilding Industry, as: but be not limited only to hull, deck, yaw rudder and radar shielding case; 2) the wind-powered electricity generation energy, as: but be not limited only to blade and cabin cover; 3) Leisure Sport, as: but be not limited only to the helmet and windsurfing; 4) automotive industry, as: but be not limited only to all kinds of roofs, windsheild and compartment; 5) building field, as: but be not limited only to top of building spare and building template; 6) agricultural and gardening, as: but be not limited only to silo dome and agricultural machinery protective cover wind-powered electricity generation material installation.
Described " large glass steelwork " is often referred to outer surface area greater than 10 square metres glass fiber reinforced plastics product, the especially outer surface area glass fiber reinforced plastics product greater than 32 square metres.These glass fiber reinforced plastics products have certain structure usually, as: cavity, plane or closed occupancy.
Embodiment
Below describe technical scheme of the present invention in detail.The embodiment of the invention is only unrestricted in order to technical scheme of the present invention to be described; Although the present invention is specified with reference to preferred embodiment; Those of ordinary skill in the art is to be understood that; Can make amendment or be equal to replacement the technical scheme of invention, and not break away from the spirit and the scope of technical scheme of the present invention, it all should be encompassed in the claim scope of the present invention.
The preparation of embodiment 1 unsaturated polyester resin
With Ucar 35, terepthaloyl moietie, m-phthalic acid and MALEIC ANHYDRIDE is polymerization single polymerization monomer, and vinylbenzene is linking agent, and H-90 exothermic peak suppressor factor, Diethyl Aniline and copper naphthenate are auxiliary agent, and preparation unsaturated polyester resin method is following:
With monomers such as Ucar 35, terepthaloyl moietie and m-phthalic acids, and in an amount of Mono-n-butyltin input of the catalyzer reaction kettle, under nitrogen protection, carry out polycondensation in 200-210 ℃.When solid acid number 20mgKOH/g is following, be cooled to below 155 ℃, in reaction kettle, add MALEIC ANHYDRIDE, continue to be warming up to 200-210 ℃ of reaction; When the solid acid number is 49-53mgKOH/g, be evacuated to vacuum tightness-80kPa.When cone-plate viscosity (No. 3 rotors, 150 ℃) is removed vacuum during for 600-690mPas and cooled off more than 175 ℃; Add to polyester that reaction obtains and to fill in the cinnamic dilution still, make unsaturated polyester resin after being cooled to 30-40 ℃.
Embodiment 2 unsaturated polyester resins and preparation of compositions thereof
With Ucar 35, terepthaloyl moietie, m-phthalic acid and MALEIC ANHYDRIDE is polymerization single polymerization monomer, and vinylbenzene is linking agent, and H-90 exothermic peak suppressor factor, Diethyl Aniline and copper naphthenate are auxiliary agent, and preparation unsaturated polyester resin method is following:
With monomers such as Ucar 35, terepthaloyl moietie and m-phthalic acids, and appropriate amount of catalysts drops in the 350L reaction kettle successively.Under nitrogen protection, begin while stirring to heat up, insulation is 1 hour when being warming up to 155-160 ℃, heats up in a steamer a temperature and is controlled at 100-102 ℃.Stop logical nitrogen in reaction kettle, and make a pressure in the reaction kettle, control reaction kettle pressure is the 1-2 crust, is warming up to 205-210 ℃ and continues to react.When reacting to solid acid number 20mgKOH/g when following, cooling also adds MALEIC ANHYDRIDE in reaction kettle, continue to be warming up to 200-205 ℃ of reaction, heats up in a steamer a temperature and is controlled at 100-102 ℃.When the solid acid number begins to vacuumize during for 48-52mgKOH/g, reach-80kPa until vacuum tightness.The vacuum tightness of maintenance-80kPa, cone-plate viscosity (No. 3 rotor 750 changes 125 ℃) 600-690mPas removes vacuum, is cooled to more than 175 ℃.The polyester that reaction is good slowly dilutes in adding cinnamic dilution still, and the dilution temperature is 65-75 ℃, will dilute the interior resin temperature of still after dilution finishes and reduce to 30-40 ℃.
Copper naphthenate, Diethyl Aniline and H-90 exothermic peak suppressor factor are added in the unsaturated polyester resin that makes, be uniformly dispersed.Sampling viscosimetric, gel time, set time and exothermic peak are done corresponding adjustment to it as required according to detected result, promptly get unsaturated polyester resin compositions.
Embodiment 3 unsaturated polyester resins and preparation of compositions thereof
With Ucar 35, terepthaloyl moietie, m-phthalic acid and MALEIC ANHYDRIDE is polymerization single polymerization monomer, and vinylbenzene is linking agent, and H-90 exothermic peak suppressor factor, Diethyl Aniline and copper naphthenate are auxiliary agent, and preparation unsaturated polyester resin method is following:
1. Ucar 35, terepthaloyl moietie, m-phthalic acid and Mono-n-butyltin are dropped in the 350L reaction kettle successively.
2. logical nitrogen (flow is 0.5m3/h) 10 minutes; Make to be in nitrogen envelope state in the reaction kettle, open to stir and begin and heat up, insulation is 1 hour when being warming up to 155-160 ℃; Logical water coolant in vertical (type) condenser immediately when heating up in a steamer water outlet, it is 100-102 ℃ that a temperature is heated up in a steamer in control.
3. stop logical nitrogen in reaction kettle, emptying device is closed, and makes to rise in the reaction kettle to press, and control reaction kettle pressure is the 1-2 crust, and insulation continues to be warming up to 205-210 ℃ of reaction after finishing.
4. when reacting to solid acid number 20mgKOH/g when following, be cooled to below 155 ℃, in reaction kettle, add MALEIC ANHYDRIDE again, continue to be warming up to 200-205 ℃ of reaction, heat up in a steamer a temperature and be controlled at 100-102 ℃.
5. when heating up in a steamer a temperature when beginning to descend, gradually reduce cooling water flow in the vertical (type) condenser until being closed to draining fully.Sampling and testing after the draining, when the solid acid number begins to vacuumize during for 48-52mgKOH/g, beginning is evacuated down to-80kPa with-1.5kPa.
6. the vacuum tightness of maintenance-80kPa is 49-53mgKOH/g until the solid acid number, and cone-plate viscosity (No. 3 rotor 750 changes 125 ℃) 600-690mPas removes vacuum, is cooled to 175 ℃.
The polyester that 7. will react good slowly dilutes in adding cinnamic dilution still, and the dilution temperature is 65-75 ℃, will dilute the interior resin temperature of still after dilution finishes and reduce to 30-40 ℃, makes unsaturated polyester resin.
8. copper naphthenate is added in the unsaturated polyester resin; Disperse after 30 minutes; Add Diethyl Aniline and H-90 exothermic peak suppressor factor, continue to disperse after 30 minutes sampling viscosimetric, gel time, set time and exothermic peak; As required it is done corresponding adjustment according to detected result, promptly get unsaturated polyester resin compositions.
Embodiment 4
Same procedure according to embodiment 3; To prepare 6 samples without each components such as Ucar 35, terepthaloyl moietie, m-phthalic acid, MALEIC ANHYDRIDE, vinylbenzene, H-90 exothermic peak suppressor factor, Diethyl Aniline and copper naphthenate of weight fraction; Be respectively: sample 1, sample 2, sample 3, sample 4, sample 5 and sample 6, the consumption of each component is referring to table 1 in the sample.These 6 sample productions are become casting matrix, and each item index that records is as shown in table 1.
Table 1
In the present embodiment, each item detects the detection of index according to as shown in table 2.
Table 2
The resin physical performance index
Can find out from table 1; The relative sample 1-4 with resistance toheat of toughness index according to the unsaturated polyester resin compositions of each component preparation of sample 5 is less better; It is lower to be mainly reflected in tensile modulus; The inflexible target of goods is relatively poor, for those tensile modulus is had the glass fiber reinforced plastics product of particular requirement, and difficulty satisfies request for utilization.
Unsaturated polyester resin compositions according to each component preparation of sample 6; Though resistance toheat obtains to improve, tensile property is still less better than sample 1-4, and physical strength is low; The rigidity of goods is too high; Easy to crack, for those tensile modulus there is the glass fiber reinforced plastics product of particular requirement, also difficulty satisfies request for utilization.
And according to the unsaturated polyester resin compositions of each component preparation of sample 1-4; Can be fit to vacuum guiding and forming technique; And the viscosity of resin is low, exothermic peak temperature is low, set time is short, physical strength is high, with the spun glass wellability good; Can not only satisfy the request for utilization of general large glass steel work, more can satisfy the request for utilization of the large glass steel work that each performance index are had relatively high expectations.
Claims (10)
1. a unsaturated polyester resin that is used for the vacuum introducing technology is characterized in that comprising following components by part by weight: Ucar 35 100-130 part, terepthaloyl moietie 3-7 part, m-phthalic acid 100-120 part, MALEIC ANHYDRIDE 60-80 part and vinylbenzene 160-200 part.
2. the unsaturated polyester resin that is used for the vacuum introducing technology according to claim 1 is characterized in that comprising following components by part by weight: Ucar 35 105-120 part, terepthaloyl moietie 4-6 part, m-phthalic acid 105-110 part, MALEIC ANHYDRIDE 65-76 part and vinylbenzene 170-190 part.
3. the unsaturated polyester resin that is used for the vacuum introducing technology according to claim 1 is characterized in that comprising following components by part by weight: 180 parts of 110 parts of Ucar 35,5 parts of terepthaloyl moietie, 105 parts of m-phthalic acids, 70 parts of MALEIC ANHYDRIDEs and vinylbenzene.
4. according to the described unsaturated polyester resin that is used for the vacuum introducing technology of one of claim 1-3, it is characterized in that described unsaturated polyester resin comprises that also weight part is the H-90 exothermic peak suppressor factor of 3-6 part.
5. according to the described unsaturated polyester resin that is used for the vacuum introducing technology of one of claim 1-3, it is characterized in that described unsaturated polyester resin comprises that also weight part is the Diethyl Aniline of 0.30-0.80 part.
6. according to the described unsaturated polyester resin that is used for the vacuum introducing technology of one of claim 1-3, it is characterized in that described unsaturated polyester resin comprises that also weight part is the copper naphthenate of 0.10-0.30 part.
7. according to the described unsaturated polyester resin that is used for the vacuum introducing technology of one of claim 1-3; It is characterized in that said unsaturated polyester resin is used for the vacuum introducing technology and produces large glass steelwork goods, the outer surface area of described large glass steelwork is greater than 10 square metres.
8. unsaturated polyester resin compositions that is used for the vacuum introducing technology is characterized in that said compsn is made up of following components by part by weight: Ucar 35 100-130 part, terepthaloyl moietie 3-7 part, m-phthalic acid 100-120 part, MALEIC ANHYDRIDE 60-80 part, vinylbenzene 160-200 part, H-90 exothermic peak suppressor factor 3-6 part, Diethyl Aniline 0.3-0.8 part and copper naphthenate 0.10-0.30 part.
9. the unsaturated polyester resin compositions that is used for the vacuum introducing technology according to claim 8 is characterized in that said compsn is made up of following components by part by weight: 0.25 part of 110 parts of Ucar 35,5 parts of terepthaloyl moietie, 105 parts of m-phthalic acids, 70 parts of MALEIC ANHYDRIDEs, 180 parts of vinylbenzene, H-90 exothermic peak inhibitors 4 .7 part, 0.45 part of Diethyl Aniline and copper naphthenate.
10. according to Claim 8 or the 9 described unsaturated polyester resin compositions that are used for the vacuum introducing technology; It is characterized in that said unsaturated polyester resin compositions is used for the vacuum introducing technology and produces large glass steelwork goods, the outer surface area of described large glass steelwork is greater than 10 square metres.
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| CN103396539A (en) * | 2013-07-22 | 2013-11-20 | 南通天和树脂有限公司 | High-reaction-activity unsaturated polyester resin and preparation method thereof |
| CN105235235A (en) * | 2015-11-06 | 2016-01-13 | 优利康达（天津）科技有限公司 | Factory building tile with bearing and light transmitting functions and forming process thereof |
| CN106881881A (en) * | 2017-03-29 | 2017-06-23 | 重庆海庆新材料有限公司 | Weather resistant glass fiber reinforced plastics product vacuum imports processing method |
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| CN102311523B (en) | 2012-11-14 |
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