CN102268168B - Composite material of unsaturated polyester resins with low styrene emission - Google Patents
Composite material of unsaturated polyester resins with low styrene emission Download PDFInfo
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- CN102268168B CN102268168B CN2010106050059A CN201010605005A CN102268168B CN 102268168 B CN102268168 B CN 102268168B CN 2010106050059 A CN2010106050059 A CN 2010106050059A CN 201010605005 A CN201010605005 A CN 201010605005A CN 102268168 B CN102268168 B CN 102268168B
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Abstract
The invention relates to a composite material of unsaturated polyester resins with low styrene emission. The composite material comprises, by weight, 10-95% of unsaturated polyesters, and 5-90% of styrene, and also comprises an inorganic layered material, a curing agent, and a promoter, and the percentages of the inorganic layered material, the curing agent, and the promoter respectively account for 1-25%, 0.1-10%, and 0.1-10% of a total weight of the unsaturated polyesters and styrene. The viscosity, the tensile strength, the impact strength, and the cure shrinkage of the composite material are 509-513MPa.s, 36-43MPa, 2.6-3.1Mpa, and 9.7-10.3% respectively. According to the invention, above technology is simple because the content of the unsaturated polyester resins is reduced by 60-80% in the storage phase period and is reduced by 40-70% in the curing phase period by comparing with no adding of a styrene emission inhibitor; and the cost is low, and the yield is high.
Description
Technical field
The present invention relates to a kind of matrix material of low-styrene volatilization unsaturated polyester resin, is the material that utilizes the low-styrene volatilization unsaturated polyester resin of inorganic lamellar material preparation specifically.
Background technology
Unsaturated polyester resin (UPR; Unsaturated PolyesterResins) has good mechanical property, electrical property and resistance to chemical corrosion; Complete processing is easy; Be widely used in glass fibre reinforcement, i.e. industries such as glass reinforced plastic, chemical anticorrosion, casted article, sanitary ware, artwork.At present, from storage, forming operation and curing characteristics and the final application performance of material cost, resin, vinylbenzene is the only monomer that unsaturated polyester resin is selected for use, and consumption generally accounts for the 40%-50% of resin total amount.Yet; Vinylbenzene vapour pressure at room temperature is higher; Volatile; Especially its special odor and under higher vapor concentration, have deleterious pungency and anesthetic action, vinylbenzene has been classified as the Hazardous substances of priority at least by the EPA of 213 countries (Environmental Proteetion Ageney).
Simultaneously, because cinnamic flash-point (34.4 ℃) is lower, can form explosive mixture (limits of explosion 1.1%-6.1%) with air under certain condition, be a potential risk in the safety in production.Cinnamic volatilization can cause unsaturated polyester and cinnamic proportioning to change, and influences the performance of UPR goods.Abroad just the volatile LSE of low-styrene (low styrene emission) resin is studied since the seventies in 20th century; Through constantly studying and test, the sporadic resin new variety of low-styrene that main in the world UPR factory commercial city has released one after another and differed from one another.
The development approach of LSE resin mainly concentrates on the following aspects at present:
1, film for additive method
In unsaturated polyester resin, adding membrane-forming agent is to suppress vinylbenzene to distribute the most frequently used method.Though membrane-forming agent suppresses cinnamic distributing, it can only solidify rank at immobilized effect just takes place.In construction process, vinylbenzene still sends in the same old way.Becoming the disadvantage of embrane method is the ply adhesion that influences in the glass reinforced plastic post forming, possibly produce delamination when particularly product is hit.
2, low-styrene-content method
Reduce styrene content in the resin, correspondingly reduced cinnamic distributing in the resin.The concentration of styrene general requirement of external low-styrene-content resin is below 35%.Reduce styrene content, resin viscosity is increased, make troubles, quality of item is descended, so must reach the purpose that reduces styrene content and don't influence other performance through new synthesis technique and chemic modified method to forming operation.
3, adopt the lower monomer of other volatility to substitute cinnamic method
In order to reduce the vinylbenzene volatility, force down not volatile new monomer segment or all replace vinylbenzene with some steams.Seeking a kind of performance can be with vinylbenzene matches in excellence or beauty, toxicity has been studied fully, originate and enrich and the monomer of reasonable price is a big difficult point.The representational new monomer of being found now is p-methylstyrene or Vinyl toluene, but its price than the high 50%-100% of vinylbenzene, these monomers can not reach the dilution properties that vinylbenzene has simultaneously.Therefore be a kind of research direction at present, do not drop into commercialization and use.
4, add the vinylbenzene oligopolymer
Reducing vinylbenzene evaporable another kind method is in resin, to add cinnamic LV oligopolymer such as PS; Can be adjusted to a lower level to cinnamic content in the resin with this oligopolymer, but PS adds phenomenons such as being prone to produce layering in the resin.
Present stage prepares the technology of low-styrene volatilization unsaturated polyester, exists production cost to increase substantially, and product performance descend, and the unsaturated polyester production technique is changed the bigger deficiency that waits.
Summary of the invention
The objective of the invention is guaranteeing product performance, change is made in original unsaturated polyester resin Production Flow Chart after, prepare the matrix material of low-styrene volatilization unsaturated polyester resin with inorganic lamellar material.
The present invention is for realizing above-mentioned purpose; The technical scheme that is adopted is: in the production process of unsaturated polyester resin, add and can suppress vinylbenzene evaporable inorganic lamellar material; Production technique through the adjustment unsaturated polyester resin; Make inorganic lamellar material and unsaturated polyester resin mix, and make unsaturated polyester, vinylbenzene, solidifying agent, promotor get into the inorganic lamellar material interlayer, the reaction heat that utilizes the unsaturated polyester that is in the inorganic lamellar material interlayer and vinylbenzene to react to emit and the growth of resultant volume; With the inorganic lamellar material limellar stripping, it is uniformly distributed in the matrix resin.The inorganic lamellar material that is uniformly distributed in the matrix resin can stop cinnamic migration; Make the evolving path of the vinylbenzene molecule in the matrix to change zigzag path into by straight line path; Increased its evolving path, reached the purpose of reduction vinylbenzene at storage stage and curing reaction stage volatile quantity thereby reduce its PQ.
A kind of matrix material of low-styrene volatilization unsaturated polyester resin is made up of unsaturated polyester, vinylbenzene, inorganic lamellar material, solidifying agent and promotor, and the weight percent of each material is: unsaturated polyester 10-95%, vinylbenzene 5-90%; The add-on of inorganic lamellar material, solidifying agent and promotor is respectively 1-25%, 0.1-10%, the 0.1-10% of unsaturated polyester and vinylbenzene gross weight.
In this technology; The volatile quantity of vinylbenzene before curing descends 75%; The cinnamic volatile quantity of cure stage descends 40%, and the viscosity of the low-styrene volatilization unsaturated polyester resin that makes is 509-513 MPa.s, and tensile strength is 36-43 MPa; Shock strength is 2.6-3.1 Mpa, and cure shrinkage is 9.7-10.3%.
Described solidifying agent is: the mixing of one or more in cyclohexanone peroxide, methylethyl ketone peroxide or the Lucidol.
Described promotor is: the mixing of one or more in epoxyeicosatrienoic acid cobalt, cobalt iso-octoate, xylidine or the Diethyl Aniline.
Described inorganic lamellar material for having the compound of laminated body structure, is one or more the combination among inorganic silicate, phosphoric acid salt, titanate, layered double-hydroxide, graphite, two chalkogenide, V2O5, the MoO3.
Described inorganic lamellar material, mean particle dia are 0.1-100 μ m, and the sheet bed thickness is 1-10nm.
Described inorganic lamellar material is the nano level lamella, is dispersed in the unsaturated polyester matrix, has played iris action, and then reaches inhibition vinylbenzene in storage and process segment evaporable purpose.
Unsaturated polyester in the described low-styrene volatilization unsaturated polyester resin composite material is for the universal glass reinforced plastic of technical grade (FRP) is used resin.
A kind of preparation method of matrix material of low-styrene volatilization unsaturated polyester resin, step is following:
One, gets vinylbenzene 5-90% and unsaturated polyester 10-95% by weight, add in the reaction vessel, mix and stirred 1-5 hour;
Two, press the gross weight of vinylbenzene and unsaturated polyester, add inorganic lamellar material 1-25% and promotor 0.1-10%, mix and stirred 1-5 hour, obtain preparatory intercalation thing;
Three, press the gross weight of vinylbenzene and unsaturated polyester, add solidifying agent 0.1-10%, post curing treatment, time 6-12 hour.
Described solidification treatment is: material is put into thermostatic drying chamber, and 40 ℃ of temperature were heating and curing 3-6 hour, and take out the back; Again material is put into drying shed, 80 ℃ of temperature were solidified 3-6 hour, eliminated the material internal residual stress, took out, and made product.
Preparing method of the present invention, can also carry out according to following steps:
Step 1, by the gross weight of vinylbenzene that configures in advance and unsaturated polyester, get the 1%-25% inorganic lamellar material of vinylbenzene and unsaturated polyester gross weight, add among the container I temperature 25-27 ℃;
Step 2, by weight in container I, add unsaturated polyester and vinylbenzene, unsaturated polyester and cinnamic add-on are: vinylbenzene 5%-90%, unsaturated polyester 10%-95%, temperature 25-27 ℃, stirring reaction 1-5 hour;
Step 3, the gross weight of pressing vinylbenzene and unsaturated polyester add promotor 0.1%-10%, temperature 25-27 ℃, stirring reaction 1-5 hour in container I;
Step 4, the gross weight of pressing vinylbenzene and unsaturated polyester add solidifying agent 0.1%-10% in container I, stirred 2-40 minute, after material is emitted;
Step 5, with the reacted material of step 4, put into the thermostatic drying chamber II, 40 ℃ of temperature were heating and curing 3-6 hour, take out the back;
Step 6, the material after step 5 solidified are put into the drying shed III, and 80 ℃ of temperature were solidified 3-6 hour, eliminated the material internal residual stress, and taking-up makes product;
In this technology; The volatile quantity of vinylbenzene before curing descends 75%; The cinnamic volatile quantity of cure stage descends 40%, and the viscosity of the low-styrene volatilization unsaturated polyester resin that makes is 509-513 MPa.s, and tensile strength is 36-43 MPa; Shock strength is 2.6-3.1 Mpa, and cure shrinkage is 9.7-10.3%.
The present invention also has following process method:
One: press the gross weight of vinylbenzene and unsaturated polyester, in container, add inorganic lamellar material 1-25% earlier, the back adds vinylbenzene 5-90%, mixes and stirs 1-5 hour, obtains preparatory intercalation thing; Add unsaturated polyester 10-95% again, the gross weight of pressing vinylbenzene and unsaturated polyester again adds promotor 0.1-10%, stirs 1-5 hour; Press the gross weight of vinylbenzene and unsaturated polyester at last; Add solidifying agent 0.1-10%, be cured processing, time 6-12 hour;
Described solidification treatment is: material is put into thermostatic drying chamber, and 40 ℃ of temperature were heating and curing 3-6 hour, and take out the back; Again material is put into drying shed, 80 ℃ of temperature were solidified 3-6 hour, eliminated the material internal residual stress, took out, and made product.
Two: get vinylbenzene 5-90% by weight and add in the container, the gross weight of pressing vinylbenzene and unsaturated polyester again adds promotor 0.1-10%, mixes and stirs 0.5-3 hour; And then the gross weight of pressing vinylbenzene and unsaturated polyester adds inorganic lamellar material 1-25%, mixes 1-5 hour, obtains preparatory intercalation thing; Add unsaturated polyester 10-95% more by weight, mix and stirred 1-5 hour, the gross weight of pressing vinylbenzene and unsaturated polyester at last adds solidifying agent 0.1-10%, is cured processing, time 6-12 hour;
Described solidification treatment is: material is put into thermostatic drying chamber, and 40 ℃ of temperature were heating and curing 3-6 hour, and take out the back; Again material is put into drying shed, 80 ℃ of temperature were solidified 3-6 hour, eliminated the material internal residual stress, took out, and made product.
Three: get vinylbenzene 5-90% by weight and add in the container; The gross weight that vinylbenzene and unsaturated polyester are pressed in the back adds solidifying agent 0.1-10%, and after the mixing, the gross weight of pressing vinylbenzene and unsaturated polyester again adds inorganic lamellar material 1-25%; Mix and stirred 1-5 hour, obtain preparatory intercalation thing; Add unsaturated polyester 10-95% again, mix and stirred 1-5 hour, the gross weight of pressing vinylbenzene and unsaturated polyester more at last adds promotor 0.1-10%, is cured processing, time 3-6 hour;
Described solidification treatment is: material is put into thermostatic drying chamber, and 40 ℃ of temperature were heating and curing 3-6 hour, and take out the back; Again material is put into drying shed, 80 ℃ of temperature were solidified 3-6 hour, eliminated the material internal residual stress, took out, and made product.
The invention has the beneficial effects as follows:
1, the cinnamic volatile quantity in the unsaturated polyester resin significantly reduces, and the unsaturated polyester resin that storage stage does not add the vinylbenzene volatilization inhibitor reduces 60%-80%, and cure stage does not reduce 40%-70% before adding the vinylbenzene volatilization inhibitor.
2, unsaturated polyester resin prepares and adds inorganic lamellar material in the process respectively and can effectively reduce cinnamic volatile quantity in the system, makes low-styrene volatilization unsaturated polyester;
3, add viscosity and the thixotropy that inorganic lamellar material can improve liquid unsaturated polyester resin;
4, aspect tensile strength and shock strength, the tensile strength and the shock strength of matrix material all make moderate progress;
5, the adding of inorganic lamellar material diminishes the shrinking percentage of material, helps guaranteeing the outer shape of cured prod;
This process means is reducing the over-all properties that the vinylbenzene evaporable has guaranteed material simultaneously, and productive rate improves more than 30%, and cost reduces 10-15%.
Embodiment
A kind of matrix material of low-styrene volatilization unsaturated polyester resin is made up of unsaturated polyester, vinylbenzene, inorganic lamellar material, solidifying agent and promotor; The weight percent that unsaturated polyester and vinylbenzene add is: unsaturated polyester 10-95%, vinylbenzene 5-90%; The weight percent that inorganic lamellar material, solidifying agent and promotor add is: the add-on of inorganic lamellar material, solidifying agent and promotor is respectively 1-25%, 0.1-10% and the 0.1-10% of unsaturated polyester and vinylbenzene gross weight; The matrix material of low-styrene volatilization unsaturated polyester resin, viscosity is 509-513 MPa.s, and tensile strength is 36-43 MPa, and shock strength is 2.6-3.1 Mpa, and cure shrinkage is 9.7-10.3%;
Described solidifying agent is: the mixing of one or more in cyclohexanone peroxide, methylethyl ketone peroxide or the Lucidol.
Described promotor is: the mixing of one or more in epoxyeicosatrienoic acid cobalt, cobalt iso-octoate, xylidine or the Diethyl Aniline.
Described inorganic lamellar material for having the compound of laminated body structure, is one or more the combination among inorganic silicate, phosphoric acid salt, titanate, layered double-hydroxide, graphite, two chalkogenide, V2O5, the MoO3.
Unsaturated polyester in the described low-styrene volatilization unsaturated polyester resin composite material is the universal unsaturated polyester of technical grade.
A kind of preparation method of matrix material of low-styrene volatilization unsaturated polyester resin, step is following:
One, gets vinylbenzene 5-90% and unsaturated polyester 10-95% by weight, add in the reaction vessel, mix and stirred 1-5 hour;
Two, press the gross weight of vinylbenzene and unsaturated polyester, add inorganic lamellar material 1-25% and promotor 0.1-10%, mix and stirred 1-5 hour, obtain preparatory intercalation thing;
Three, press the gross weight of vinylbenzene and unsaturated polyester, add solidifying agent 0.1-10%, post curing treatment, time 6-12 hour.
Described solidification treatment is: material is put into thermostatic drying chamber, and 40 ℃ of temperature were heating and curing 3-6 hour, and take out the back; Again material is put into drying shed, 80 ℃ of temperature were solidified 3-6 hour, eliminated the material internal residual stress, took out, and made product.
The present invention, also can adopt following steps to carry out:
Step 1, the gross weight of pressing vinylbenzene and unsaturated polyester are got inorganic lamellar material 1%-25%, add among the container I, and be temperature 25-27 ℃, subsequent use;
Step 2, by weight in container I, add unsaturated polyester and vinylbenzene, unsaturated polyester and cinnamic add-on are: vinylbenzene 5%-90%, unsaturated polyester 10%-95%, mixes and stirred 1-5 hour by temperature 25-27 ℃;
Step 3, the gross weight of pressing vinylbenzene and unsaturated polyester in container I, add promotor 0.1%-10%, temperature 25-27 ℃, stir 1-5 hour;
Step 4, the gross weight of pressing vinylbenzene and unsaturated polyester add solidifying agent 0.1%-10% in container I, stirred 2-40 minute, after material is emitted;
Step 5, with the material that step 4 makes, put into the thermostatic drying chamber II, 40 ℃ of temperature were heating and curing 3-6 hour, take out the back;
Step 6, the material after step 5 solidified are put into the drying shed III, and 80 ℃ of temperature were solidified 3-6 hour, eliminated the material internal residual stress, and taking-up makes product;
In this technology, the volatile quantity of vinylbenzene before curing descends 75%, and the cinnamic volatile quantity of cure stage descends 40%; The viscosity of the low-styrene volatilization unsaturated polyester resin that makes is 510 MPa.s; Tensile strength is 36 MPa, and shock strength is 2.6 Mpa, and cure shrinkage is 9.7%.
Below in conjunction with instance the present invention is done further detailed description
Embodiment 1
Step 1, get vinylbenzene 600kg and unsaturated polyester 400kg by weight, add in the reaction vessel, mix and stirred 1-5 hour;
Step 2, the gross weight of pressing vinylbenzene and unsaturated polyester add inorganic lamellar material 100kg and promotor 10kg in reaction vessel, mix and stirred 1-5 hour, obtain preparatory intercalation thing;
Step 3, the gross weight of pressing vinylbenzene and unsaturated polyester add solidifying agent 10kg in reaction vessel, stirred 2-40 minute, and material is emitted;
Step 4, material is sent in the thermostatic drying chamber, 40 ℃ of temperature were heating and curing 3-6 hour, and take out the back;
Step 5, again material is put into drying shed, 80 ℃ of temperature were solidified 3-6 hour, eliminated the material internal residual stress, took out, and made product.
In this technology, the volatile quantity of vinylbenzene before curing descends 75%, and the cinnamic volatile quantity of cure stage descends 40%; The viscosity of the low-styrene volatilization unsaturated polyester resin that makes is 510 MPa.s; Tensile strength is 38 MPa, and shock strength is 2.5 Mpa, and cure shrinkage is 9.5%.
Embodiment 2
Step 1, get vinylbenzene 400kg and unsaturated polyester 600kg by weight, add in the reaction vessel, mix and stirred 1-5 hour;
Step 2, the gross weight of pressing vinylbenzene and unsaturated polyester add inorganic lamellar material 250kg in reaction vessel, promotor 100kg mixes and stirred 1-5 hour, obtains preparatory intercalation thing;
Step 3, the gross weight of pressing vinylbenzene and unsaturated polyester add solidifying agent 100kg in reaction vessel, stirred 2-40 minute, and material is emitted;
Step 4, material is sent in the thermostatic drying chamber, 40 ℃ of temperature were heating and curing 3-6 hour, and take out the back;
Step 5, again material is put into drying shed, 80 ℃ of temperature were solidified 3-6 hour, eliminated the material internal residual stress, took out, and made product.
In this technology, the volatile quantity of vinylbenzene before curing descends 75%, and the cinnamic volatile quantity of cure stage descends 40%; The viscosity of the low-styrene volatilization unsaturated polyester resin that makes is 511 MPa.s; Tensile strength is 37 MPa, and shock strength is 2.6 Mpa, and cure shrinkage is 9.7%.
Embodiment 3
Step 1, get vinylbenzene 350kg, unsaturated polyester 650kg, subsequent use; Press the gross weight of vinylbenzene and unsaturated polyester, get inorganic lamellar material 250kg, add in the reaction vessel I;
Step 2, in reaction vessel I, add vinylbenzene 350 kg and unsaturated polyester 650kg, mix and end;
Step 3, in reaction vessel I, add promotor epoxyeicosatrienoic acid cobalt 10kg, temperature 25-27 ℃, hybrid reaction 1-5 hour;
Step 4, in reaction vessel I, add solidifying agent cyclohexanone peroxide 10kg, after mixing, reacted 1-5 hour;
Step 5, the reacted material of step 4 is put into the thermostatic drying chamber II, 40 ℃ of temperature were solidified 3-6 hour;
Step 6, the material after step 5 solidified are put into the drying shed III, and 80 ℃ of temperature were solidified 3-6 hour, eliminated the material internal residual stress, and taking-up makes product;
In this technology, the volatile quantity of vinylbenzene before curing descends 75%, and the cinnamic volatile quantity of cure stage descends 40%; The viscosity of the low-styrene volatilization unsaturated polyester resin that makes is 510 MPa.s; Tensile strength is 36 MPa, and shock strength is 2.6 Mpa, and cure shrinkage is 9.7%.
Embodiment 4
Step 1, get vinylbenzene 650kg, unsaturated polyester 350kg, subsequent use; Press the gross weight of vinylbenzene and unsaturated polyester, get inorganic lamellar material 10kg, add in the reaction vessel I;
Step 2, in reaction vessel I, add vinylbenzene 650 kg and unsaturated polyester 350kg, mix and end;
Step 3, in reaction vessel I, add promotor epoxyeicosatrienoic acid cobalt and xylidine 100kg, temperature 25-27 ℃, hybrid reaction 1-5 hour; The weight ratio that epoxyeicosatrienoic acid cobalt and xylidine add is: 1 ︰ 1;
Step 4, in reaction vessel I, add solidifying agent cyclohexanone peroxide and Potassium peroxide 85 ketone 100kg, after mixing, reacted 1-5 hour; Cyclohexanone peroxide and the Potassium peroxide 85 weight ratio of ketone adding are: 1 ︰ 1;
Step 5, the reacted material of step 4 is put into the thermostatic drying chamber II, 40 ℃ of temperature were solidified 3-6 hour;
Step 6, the material after step 5 solidified are put into the drying shed III, and 80 ℃ of temperature were solidified 3-6 hour, eliminated the material internal residual stress, and taking-up makes product;
In this technology, the volatile quantity of vinylbenzene before curing descends 75%, and the cinnamic volatile quantity of cure stage descends 40%; The viscosity of the low-styrene volatilization unsaturated polyester resin that makes is 510 MPa.s; Tensile strength is 36 MPa, and shock strength is 2.6 Mpa, and cure shrinkage is 9.7%.
Embodiment 5
Step 1, get vinylbenzene 700kg, unsaturated polyester 300kg, subsequent use; With vinylbenzene 700kg, add among the reaction vessel I earlier;
Step 2, inorganic silicate and phosphoric acid salt 100kg in reaction vessel I in the adding inorganic lamellar material, stirring reaction 1-5 hour, make material obtain preparatory intercalation thing by temperature 25-27 ℃; The weight ratio that inorganic silicate and phosphoric acid salt add is: 1 ︰ 1;
Step 3, in reaction vessel I, add promotor cobalt iso-octoate 50kg, stirred 2-10 minute;
Step 4, in reaction vessel I, add unsaturated polyester 300kg, stirring reaction 1-5 hour;
Step 5, in reaction vessel I, add solidifying agent Lucidol 50kg, stirred 20-40 minute, after material is emitted;
Step 6, the material after step 5 solidified are put into the thermostatic drying chamber II, and 40 ℃ of temperature were solidified 3-6 hour, after material is emitted;
Step 7, the material after step 6 solidified are put into the drying shed III, and 80 ℃ of temperature were solidified 3-6 hour, eliminated the material internal residual stress, and taking-up makes product;
In this technology, the volatile quantity of vinylbenzene before curing descends 80%, and the cinnamic volatile quantity of cure stage descends 46%; The viscosity of the low-styrene volatilization unsaturated polyester resin that makes is 509 MPa.s; Tensile strength is 40 MPa, and shock strength is 2.9Mpa, and cure shrinkage is 10.2%.
Embodiment 6
Step 1, get vinylbenzene 500kg, unsaturated polyester 500kg, subsequent use; With vinylbenzene 500kg, add among the reaction vessel I earlier;
Step 2, inorganic silicate, phosphoric acid salt, phosphoric acid salt and layered double-hydroxide 200kg in reaction vessel I in the adding inorganic lamellar material, stirring reaction 1-5 hour, make material obtain preparatory intercalation thing by temperature 25-27 ℃; The weight ratio that inorganic silicate, phosphoric acid salt, phosphoric acid salt and layered double-hydroxide add is: 1 ︰, 1 ︰, 1 ︰ 1;
Step 3, in reaction vessel I, add promotor cobalt iso-octoate, xylidine and epoxyeicosatrienoic acid cobalt 30kg, stirred 2-10 minute; The weight ratio that cobalt iso-octoate, xylidine and epoxyeicosatrienoic acid cobalt add is: 1 ︰, 1 ︰ 1;
Step 4, in reaction vessel I, add unsaturated polyester 500kg, stirring reaction 1-5 hour;
Step 5, in reaction vessel I, add solidifying agent Lucidol, cyclohexanone peroxide and methylethyl ketone peroxide 30kg, stirred 20-40 minute, after material is emitted; The weight ratio of the adding of Lucidol, cyclohexanone peroxide and methylethyl ketone peroxide is: 1 ︰, 1 ︰ 1;
Step 6, the material after step 5 solidified are put into the thermostatic drying chamber II, and 40 ℃ of temperature were solidified 3-6 hour, after material is emitted;
Step 7, the material after step 6 solidified are put into the drying shed III, and 80 ℃ of temperature were solidified 3-6 hour, eliminated the material internal residual stress, and taking-up makes product;
In this technology, the volatile quantity of vinylbenzene before curing descends 80%, and the cinnamic volatile quantity of cure stage descends 46%; The viscosity of the low-styrene volatilization unsaturated polyester resin that makes is 509 MPa.s; Tensile strength is 40 MPa, and shock strength is 2.9Mpa, and cure shrinkage is 10.2%.
Embodiment 7
Step 1, get vinylbenzene 200kg, unsaturated polyester 800kg, subsequent use; Behind vinylbenzene 200kg adding reaction vessel I, add promotor Diethyl Aniline 20kg again, mix and stirred 30-60 minute;
Step 2, layered double-hydroxide and graphite 150kg in reaction vessel I in the adding inorganic lamellar material, stirring reaction 1-5 hour, make material obtain preparatory intercalation thing by temperature 25-27 ℃; The weight ratio that layered double-hydroxide and graphite add is: 1 ︰ 1;
Step 3, in reaction vessel I, add unsaturated polyester 800kg, stirring reaction 1-5 hour;
Step 4, in reaction vessel I, add solidifying agent methylethyl ketone peroxide 20kg, stirred 20-40 minute;
Step 5, the material after step 4 solidified are put into the thermostatic drying chamber II, and 40 ℃ of temperature were heating and curing 3-6 hour, and take out the back;
Step 6, the material after step 5 solidified are put into the drying shed III, and 80 ℃ of temperature were solidified 3-6 hour, eliminated the material internal residual stress, and taking-up makes product;
In this technology, the volatile quantity of vinylbenzene before curing descends 70%, and cure stage vinylbenzene volatile quantity descends 43%; The viscosity of the low-styrene volatilization unsaturated polyester resin that makes is 511MPa.s; Tensile strength is 38 MPa, and shock strength is 2.5Mpa, and cure shrinkage is 9.0%.
Embodiment 8
Step 1, get vinylbenzene 900kg, unsaturated polyester 100kg, subsequent use; To vinylbenzene 900kg is added in the reaction vessel I;
Step 2, cyclohexanone peroxide, methylethyl ketone peroxide and Lucidol 60kg in reaction vessel I in the adding solidifying agent mix and stirred 30-60 minute; The adding weight ratio of cyclohexanone peroxide, methylethyl ketone peroxide and Lucidol is: 1 ︰, 1 ︰ 1;
Step 3, in reaction vessel I, add inorganic lamellar material 150kg, temperature 25-27 ℃, stirred 1-5 hour, obtain preparatory intercalation thing; Described inorganic lamellar material is made up of inorganic silicate, phosphoric acid salt, titanate, layered double-hydroxide, graphite and two chalkogenide, and the adding weight ratio of each material is: 1 ︰, 1 ︰, 1 ︰, 1 ︰, 1 ︰ 1;
Step 4, in reaction vessel I, add unsaturated polyester 100kg, stirring reaction 1-5 hour;
Step 5, in reaction vessel I, add promotor 45kg, stirred 20-40 minute; Described promotor is made up of epoxyeicosatrienoic acid cobalt, cobalt iso-octoate, xylidine and Diethyl Aniline, and the adding weight ratio of each material is: 1 ︰, 1 ︰, 1 ︰ 1;
Step 6, the reacted material of step 5 is put into the thermostatic drying chamber II, 40 ℃ of temperature were heating and curing 3-6 hour, and take out the back;
Step 7, the material after step 6 solidified are put into the drying shed III, and 80 ℃ of temperature were solidified 3-6 hour, eliminated the material internal residual stress, and taking-up makes product;
In this technology, the volatile quantity of vinylbenzene before curing descends 67%, and cure stage vinylbenzene volatile quantity descends 49%; The viscosity of the low-styrene volatilization unsaturated polyester resin that makes is 513 MPa.s; Tensile strength is 43MPa, and shock strength is 3.1Mpa, and cure shrinkage is 10.3%.
Claims (4)
1. the matrix material of a low-styrene volatilization unsaturated polyester resin is characterized in that: be made up of unsaturated polyester, vinylbenzene, inorganic lamellar material, solidifying agent and promotor; Unsaturated polyester and cinnamic weight percent are: unsaturated polyester 10-95%, vinylbenzene 5-90%; The weight percent of inorganic lamellar material, solidifying agent and promotor is: the add-on of inorganic lamellar material, solidifying agent and promotor is respectively 1-25%, 0.1-10% and the 0.1-10% of unsaturated polyester and vinylbenzene gross weight; The matrix material of said low-styrene volatilization unsaturated polyester tree, viscosity is 509-513 mPa.s, and tensile strength is 36-43 MPa, and shock strength is 2.6-3.1 Mpa, and cure shrinkage is 9.7-10.3%;
Described solidifying agent is: the mixing of one or more in cyclohexanone peroxide, methylethyl ketone peroxide or the Lucidol;
Described promotor is: the mixing of one or more in epoxyeicosatrienoic acid cobalt, cobalt iso-octoate, xylidine or the Diethyl Aniline;
Described inorganic lamellar material for having the compound of laminated body structure, is one or more the combination in inorganic silicate, phosphoric acid salt, titanate, layered double-hydroxide, graphite and the two chalkogenide;
Described inorganic lamellar material is the nano level lamella, is dispersed in the unsaturated polyester resin matrix, and mean particle dia is 0.1-100 μ m, and the sheet bed thickness is 1-10nm.
2. the matrix material of a kind of low-styrene volatilization unsaturated polyester resin according to claim 1, it is characterized in that: described unsaturated polyester is the universal glass reinforced plastic FRP of technical grade resin.
3. the preparation method of the matrix material of a kind of low-styrene volatilization unsaturated polyester resin according to claim 1, step is following:
One, gets vinylbenzene 5-90% and unsaturated polyester 10-95% by weight, add in the reaction vessel, mix and stirred 1-5 hour;
Two, press the gross weight of vinylbenzene and unsaturated polyester, add inorganic lamellar material 1-25% and promotor 0.1-10%, mix and stirred 1-5 hour, obtain preparatory intercalation thing;
Three, press the gross weight of vinylbenzene and unsaturated polyester, add solidifying agent 0.1-10%, solidification treatment 6-12 hour.
4. the preparation method of the matrix material of a kind of low-styrene volatilization unsaturated polyester resin according to claim 3, it is characterized in that: described solidification treatment is: material is put into thermostatic drying chamber, and 40 ℃ of temperature were heating and curing 3-6 hour, and take out the back; Again material is put into drying shed, 80 ℃ of temperature were solidified 3-6 hour, eliminated the material internal residual stress, took out, and made product.
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| CN103360921B (en) * | 2012-03-28 | 2015-12-16 | 展辰涂料集团股份有限公司 | A kind of unsaturated polyester coatings for furniture of anti-greening |
| CN102924666A (en) * | 2012-10-15 | 2013-02-13 | 深圳大学 | Polymer/clay nano-composite material, preparation method thereof and nano-GFRP (Glass Fiber Reinforced Polymer) composite material |
| CN104072682B (en) * | 2014-06-27 | 2016-06-22 | 济南轨道交通装备有限责任公司 | A kind of bullet train toilet composite material casing and preparation method thereof |
| CN105524443A (en) * | 2016-01-27 | 2016-04-27 | 合肥瑞瑶环保建材科技有限公司 | High-strength glass fiber reinforced plastic septic tank and preparation method thereof |
| CN110194887B (en) * | 2019-06-19 | 2021-04-27 | 常州华科聚合物股份有限公司 | Styrene volatilization inhibitor based on cholesterol derivative and preparation method thereof |
| CN111333876A (en) * | 2020-01-06 | 2020-06-26 | 泰州市中盛机电有限公司 | Resin mixing method |
| CN113388240B (en) * | 2021-06-15 | 2023-05-09 | 威驰腾(福建)汽车有限公司 | Graphite felt composite material and forming method thereof |
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| CN101845208A (en) * | 2010-05-19 | 2010-09-29 | 厦门大学 | Unsaturated polyester resin composite material and preparation method thereof |
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| US6166097A (en) * | 1999-04-14 | 2000-12-26 | Nippon Shokubai Co., Ltd. | Method for production of porous material |
| CN1291625A (en) * | 2000-10-28 | 2001-04-18 | 河北工业大学 | Nm-class unsaturated polyester/montmorillonite composition and its preparing process |
| CN101613442A (en) * | 2009-07-21 | 2009-12-30 | 常州市华润复合材料有限公司 | A kind of suitable large glass steel construction layer is with hanging down volatilization unsaturated polyester resin and method for making thereof |
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