CN107663264A - A kind of unsaturated polyester resin without styrene and preparation method and application - Google Patents
A kind of unsaturated polyester resin without styrene and preparation method and application Download PDFInfo
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- CN107663264A CN107663264A CN201710858285.6A CN201710858285A CN107663264A CN 107663264 A CN107663264 A CN 107663264A CN 201710858285 A CN201710858285 A CN 201710858285A CN 107663264 A CN107663264 A CN 107663264A
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- Prior art keywords
- unsaturated polyester
- styrene
- polyester resin
- preparation
- monomer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44B—BUTTONS, PINS, BUCKLES, SLIDE FASTENERS, OR THE LIKE
- A44B1/00—Buttons
- A44B1/02—Buttons characterised by their material
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The present invention provides a kind of unsaturated polyester resin without styrene and preparation method and application.The preparation method includes under an inert atmosphere, acrylate monomers, polymerization inhibitor and catalyst being well mixed, obtain compound；Isocyanate-monomer is added into the compound again so that acrylate monomers react with isocyanate-monomer, terminates until being reacted when being free of isocyano in system, obtains more pi-allyl urethane type addition products；Unsaturated polyester (UP) without styrene, more pi-allyl urethane type addition products and acrylic cross-linking monomer are well mixed, obtain unsaturated polyester (UP)/linked system；Initiator is added into the system again, after being well mixed, gained mixture is solidified, obtains the unsaturated polyester resin for being free of styrene.Compared with using the unsaturated polyester resin of Styrene solidification, unsaturated polyester resin of the invention has suitable therewith processing characteristics and mechanical property, and has more excellent impact property.
Description
Technical field
The present invention relates to a kind of unsaturated polyester resin without styrene and preparation method and application, it is auxiliary to belong to clothes
Material material and its preparing technical field.
Background technology
At present, the Polyester button used in this area is using unsaturated polyester resin as primary raw material, using styrene as friendship
Join curing component and diluent, add appropriate additive, carry out gel in particular device and mould, curing molding is pearly-lustre
Or the sheet material or bar of non-pearly-lustre, then it is manufactured through a series of machining and surface treatment.Wherein, unsaturated polyester tree
The button that fat makes has the characteristics of acid and alkali-resistance and high temperature resistant are laundered, and color is full of variety, and physicochemical property is excellent, extensive use
It is the leading products of clothes button in dress accessory.
During unsaturated polyester (UP) is used as main material production thermosetting polyester button, the dosage of styrene reaches
30%, even more high.And the vapour pressure of styrene at room temperature is higher, readily volatilized, and there is irritating special odor,
There is stimulation to eyes and upper respiratory tract mucosa, therefore its volatility and toxic side effect will necessarily be good for environment and operating personnel
Kang Zaocheng greatly endangers.
It is used as linked and the diluent institute of unsaturated polyester (UP) in order to reduce or even eliminate current this area by styrene
Caused negative effect is, it is necessary to select or design the crosslinking list of the unsaturated polyester (UP) small with synthesis volatility and toxic side effect
Body, to substitute traditional styrene, so that the material of Polyester button and preparation process have environment-friendly characteristic, so as to significantly
Ground improves manufacturing enterprise and the working environment of operating personnel, ensures their health；Meanwhile eliminate volatilization and the residual of styrene
To harmful effect caused by ecological environment.
Therefore, the health of harm caused by how eliminating styrene, improvement working condition, environmental protection and operating personnel are
It is urgently to be resolved hurrily as manufacturing enterprise faced one of Polyester button manufacturing enterprise, or even thermosetting unsaturated polyester material
Problem.
The content of the invention
In order to solve the shortcomings that above-mentioned and deficiency, it is an object of the invention to provide a kind of unsaturation without styrene to gather
The preparation method of ester resin.
The present invention also aims to provide the unsaturated polyester (UP) without styrene being prepared by above-mentioned preparation method
Resin.
The present invention also aims to provide the above-mentioned unsaturated polyester resin without styrene in Polyester button is prepared
Application.
The present invention also aims to provide a kind of Polyester button, it is by the above-mentioned unsaturated polyester (UP) tree without styrene
What fat was prepared.
To reach above-mentioned purpose, the present invention provides a kind of preparation method of the unsaturated polyester resin without styrene, its
Comprise the following steps：
(1), under an inert atmosphere, acrylate monomers, polymerization inhibitor and catalyst are well mixed, obtain compound；
Isocyanate-monomer is added into the compound so that acrylate monomers react with isocyanate-monomer, until body again
Reaction terminates when isocyano is free of in system, obtains more pi-allyl urethane type addition products；
(2), by the unsaturated polyester (UP) without styrene, step (1) more pi-allyl urethane type addition products and acrylic acid
Class cross-linking monomer is well mixed, and obtains unsaturated polyester (UP)/linked system；
(3) initiator, is added into step (2) unsaturated polyester (UP)/linked system, after being well mixed, by institute
Obtain mixture to be solidified, obtain the unsaturated polyester resin for being free of styrene.
According to specific embodiments of the present invention, step (1) is described to be well mixed to realize by stirring at room temperature, this
Outside, it is also required to be stirred after adding isocyanate-monomer, wherein, stirring used is this area routine techniques in step (1)
Means.
According to specific embodiments of the present invention, the measure of isocyano and its contain in the preparation method, in step (1)
The judgement of amount specifically includes following steps：During the course of the reaction, sampled every 1 hour, determine (using infrared spectrometer) isocyanide
The content of acid group (- NCO), untill being free of isocyano in system.
According to specific embodiments of the present invention, step (3) described initiator adds under room temperature, stirring condition, adds
By continuing stirring it can be made to be well mixed with unsaturated polyester (UP)/linked system after entering；
In addition, step (3) described solidification can be carried out in the traditional dies of this area.
According to specific embodiments of the present invention, in described preparation method, it is preferable that the acrylate monomers bag
Include hydroxy-ethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), hydroxypropyl acrylate (HPA) and methacrylic acid hydroxypropyl
One or more of combinations in ester (HPMA).If the acrylate monomers include combination several in above-mentioned substance,
They can be used in mixed way with arbitrary proportion.
According to specific embodiments of the present invention, in described preparation method, it is preferable that the isocyanate-monomer includes
Toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), the isocyanate of hexa-methylene two (HDI), different Fo Er
One or more of combinations in ketone diisocyanate (IPDI), PPDI and 1,4- cyclohexane diisocyanates.
If the isocyanate-monomer includes combination several in above-mentioned substance, they can be used in mixed way with arbitrary proportion.
According to specific embodiments of the present invention, in described preparation method, it is preferable that the polymerization inhibitor is included to benzene two
One kind or any two kinds of combination in phenol, methyl hydroquinone, TBHQ.If the polymerization inhibitor includes above-mentioned thing
Two kinds of combination in matter, then they can be used in mixed way with arbitrary proportion.
According to specific embodiments of the present invention, in described preparation method, it is preferable that the catalyst includes tetramethyl
One or more of combinations in butylamine, triethylene diamine, tin dilaurate dibutene base tin and stannous octoate.If the catalyst
Including combination several in above-mentioned substance, then they can be used in mixed way with arbitrary proportion.
According to specific embodiments of the present invention, in described preparation method, it is preferable that the acrylate monomers and
The dosage of isocyanate-monomer respectively in terms of hydroxyl (- OH) and isocyano (- NCO), wherein, mole of hydroxyl and isocyano
Than for 1.03-1.1；
Counted using the gross mass of acrylate monomers and isocyanate-monomer as 100%, the dosage of the polymerization inhibitor is
0.005-0.1%, the dosage of catalyst is 0.05-0.5%.
According to specific embodiments of the present invention, in described preparation method, it is preferable that temperature is reacted described in step (1)
Spend for 55-65 DEG C.
According to specific embodiments of the present invention, in described preparation method, it is preferable that unsaturation used in step (2)
Polyester includes O-phthalic acid type unsaturated polyester (UP), M-phthalic acid type unsaturated polyester (UP) and terephthaldehyde's acid type unsaturated polyester (UP)
In one or more of combinations.Wherein, O-phthalic acid type unsaturated polyester (UP), M-phthalic acid type unsaturated polyester (UP) and to benzene
Diformazan acid type unsaturated polyester (UP) is that this area uses conventional substances, and any synthesis or the commercially available product may be incorporated for this
Invention.
According to specific embodiments of the present invention, in described preparation method, it is preferable that the acrylic cross-linking monomer
Including the propylene of hexylene glycol two (HDDA), tripropylene glycol diacrylate (TPGDA), diethylene glycol diacrylate
(DEGDA), one kind in trimethylolpropane trimethacrylate (TMPTA), TEGDMA (TEGDMA)
Or several combination.If the acrylic cross-linking monomer includes combination several in above-mentioned substance, they can arbitrarily compare
Example is used in mixed way.
According to specific embodiments of the present invention, in described preparation method, it is preferable that with unsaturated polyester (UP)/crosslinking group
The gross mass of split system is 100% meter, in the unsaturated polyester (UP)/linked system, the quality percentage of unsaturated polyester (UP)
Number is 40-70%, and the mass percents of more pi-allyl urethane type addition products is 5-30%, the quality hundred of acrylic cross-linking monomer
Fraction is 20-50%.
According to specific embodiments of the present invention, in described preparation method, it is preferable that step (2) is described well mixed
It is to be realized by stirring 3-4 hours at 70-80 DEG C.
According to specific embodiments of the present invention, in described preparation method, it is preferable that the initiator includes peroxidating
MEK (MEKP), cyclohexanone peroxide, benzoyl peroxide (BPO), dilauroyl peroxide (LPO), isopropyl benzene hydroperoxide
(CHP), azodiisobutyronitrile (AIBN), ABVN (ABVN), the benzoyl peroxide tert-butyl ester (TBPB) and double (uncles 4-
Butylcyclohexyl) one or more of combinations in peroxy dicarbonate.If the initiator includes several in above-mentioned substance
Combination, then they can be used in mixed way with arbitrary proportion.
According to specific embodiments of the present invention, in described preparation method, it is preferable that with the unsaturated polyester (UP)/friendship
The gross weight number for joining component mixture is 100 meters, and the dosage of the initiator is 0.1-4.0 parts by weight.
According to specific embodiments of the present invention, in described preparation method, it is preferable that the solidification temperature is 25-100
DEG C, hardening time 10-30min.
According to specific embodiments of the present invention, in described preparation method, it is preferable that step (3) is also to the mixing
Accelerator is added in thing.
According to specific embodiments of the present invention, in described preparation method, it is preferable that the accelerator includes isooctyl acid
One kind in cobalt, cobalt naphthenate, manganese naphthenate, vanadium iso-octoate, dimethylaniline, diethylaniline and dimethyl-p-toluidine or
Any two kinds of combination.If the accelerator includes combination several in above-mentioned substance, they can be mixed with arbitrary proportion makes
With.
According to specific embodiments of the present invention, in described preparation method, it is preferable that with the unsaturated polyester (UP)/friendship
The gross weight number for joining component mixture is 100 meters, and the dosage of the accelerator is 0.1-2.0 parts by weight.
It is prepared not present invention also offers the preparation method by the above-mentioned unsaturated polyester resin without styrene
Unsaturated polyester resin containing styrene.
According to specific embodiments of the present invention, it is preferable that should the tensile strength without the unsaturated polyester resin of styrene
For 35-50MPa, bending strength 45-75MPa, impact strength 6-18KJ/m2, heat distortion temperature is 40-55 DEG C, and fracture is stretched
Long rate is 2.5-6.0%.
Present invention also offers application of the above-mentioned unsaturated polyester resin without styrene in Polyester button is prepared.
Present invention also offers a kind of Polyester button, and it is prepared into by the unsaturated polyester resin without styrene
Arrive.
The preparation method of unsaturated polyester resin provided by the present invention without styrene is with the insatiable hunger without styrene
It is base stock with polyester, a kind of new type functional synthesized with the reaction by acrylate monomers and isocyanate-monomer
The more pi-allyl urethane type addition products of reactivity are the first linked, will be certain using acrylate monomer as the second linked
The unsaturated polyester (UP) of ratio/more pi-allyls urethane type addition product/acrylate monomer is mixed under certain condition
Resin system；Appropriate initiator and accelerator are added into the hybrid resin system again, it is then solid at a proper temperature
Chemical conversion type, so as to which the unsaturated polyester resin material without styrene be made.
As can be seen here, preparation method provided by the present invention is completely without using the linked benzene of traditional unsaturated polyester (UP)
Ethene, it is not required that the preparation technology of unsaturated polyester resin is significantly adjusted or changes, it is available with synthesis by selecting, designing
Make the new linked of unsaturated polyester (UP), successfully have developed the unsaturated polyester resin without styrene.And the system
Preparation Method does not use the environment-friendly method of styrene completely to be a kind of, the preparation method can significantly improve manufacturing enterprise and
The working environment of operating personnel, ensure their health；Meanwhile it can also eliminate the volatilization of styrene and residual to ecological ring
Harmful effect caused by border.
Specifically, the unsaturated polyester resin of the Styrene solidification conventional with this area and in general low-styrene be not
Saturated polyester resin is compared, and the preparation method of the unsaturated polyester resin provided by the present invention without styrene has following excellent
Point：
(1) preparation method selects the unsaturated polyester (UP) for being entirely free of styrene, and with not volatile more pi-allyl ammonia
Ester type addition product and linked and diluent that acrylic ester monomer is unsaturated polyester (UP), instead of styrene, make completely
It is standby gone out the excellent unsaturated polyester resin without styrene of physical and mechanical properties, improve unsaturated polyester resin material or
The production environment of the manufacturing enterprise of product, the volatilization of styrene is eliminated to the health of worker and the negative effect of ecological environment；
(2) in the preparation method, it can be used as the more allyls of new type functional reactivity of the linked of unsaturated polyester (UP)
The synthesis of base urethane type addition product is simple and easy, and raw material is easy to get, and product does not need any purifying, can be used directly, and also can make
Use, this is very beneficial for the serialization of the production technology of the unsaturated polyester resin without styrene.
Compared with traditional unsaturated polyester resin using Styrene solidification, the present invention is preparation-obtained to be free of benzene second
The unsaturated polyester resin of alkene has suitable therewith processing characteristics and mechanical property, and it has more excellent impact
Energy.In the specific embodiment of the invention, the unsaturation of styrene is free of to this according to the method for GBT2567-2008 defineds
Polyester resin carries out performance test, and it is 35-50MPa, bending strength 45-75MPa, impact strength 6- to measure its tensile strength
18KJ/m2, elongation at break 2.5-6.0%；Method according to GB/T1634-1989 defineds tests this and is free of styrene
The heat distortion temperature of unsaturated polyester resin, test result show that its heat distortion temperature is 40-55 DEG C.
Brief description of the drawings
Fig. 1 is raw materials used hydroxy-ethyl acrylate (HEA), methyl diphenylene diisocyanate in the embodiment of the present invention 1
(MDI) and preparation-obtained more pi-allyl urethane type addition products (HEA-MDI) infared spectrum.
Embodiment
In order to which technical characteristic, purpose and the beneficial effect of the present invention is more clearly understood, in conjunction with detail below
Embodiment to technical scheme carry out it is described further below, but it is not intended that to the present invention can practical range limit
It is fixed.
Embodiment 1
A kind of preparation method of the unsaturated polyester resin without styrene is present embodiments provided, it is included in detail below
Step：
(1), the synthesis of more pi-allyl urethane type addition products：
In the reaction vessel (conventional reactor that this area uses) with stirring, hydroxy-ethyl acrylate is sequentially added
(HEA) 51.1 grams, 0.101 gram of 0.011 gram of hydroquinones and tin dilaurate dibutene base tin, under conditions of room temperature, logical nitrogen
Stir；Then, 50 grams of methyl diphenylene diisocyanates (MDI) are added, are warming up to 55-65 DEG C, and are stirred, make hydroxyl third
Acrylic monomer reacts with isocyanate-monomer, is sampled during the course of the reaction every 1 hour, with determination of infrared spectroscopy isocyanide
The content of acid group (- NCO), untill being free of isocyano in system, that is, more pi-allyl urethane type addition products are made, are designated as
HEA-MDI。
Wherein, more pi-allyl urethane type adduct HEA-MDI made from the present embodiment and 2 kinds of raw materials of the adduct are synthesized
HEA and MDI infared spectrum is as shown in figure 1, from figure 1 it appears that the characteristic absorption peak of NCO is located in MDI
2274cm-1, but with the progress of reaction, the characteristic peak at this is gradually decrease to disappear, and this shows that NCO disappears completely
Consumption, it is possible to determine that synthesized the set goal product HEA-MDI.
(2), the mixing of unsaturated polyester (UP)/linked system：
In the reaction vessel (conventional reactor that this area uses) with stirring, 90 grams of phthalic acid is sequentially added
Unsaturated polyester resin DS988 (Nantong Tianhe Resin Co., Ltd.), 40 grams of the HEA-MDI of type, 70 grams of hexylene glycol dipropyl
Alkene ester (HDDA), 3-4 hours are stirred at a temperature of 70-80 DEG C, until DS988/HEA-MDI/HDDA systems are mixed thoroughly.
(3), the curing molding of the unsaturated polyester resin without styrene：
100 parts of the uniform DS988/HEA-MDI/HDDA resins prepared in step (2) are taken, in room temperature, stirring condition
1.5 parts of cobalt iso-octoates of lower addition and 2.0 parts of methyl ethyl ketone peroxides, and stir；By this containing the DS988/ for triggering system
HEA-MDI/HDDA mixtures import mould, solidify the regular hour under room temperature (about 25 DEG C), you can are made and are free of styrene
Unsaturated polyester resin material, be designated as materials A.
Embodiment 2
A kind of preparation method of the unsaturated polyester resin without styrene is present embodiments provided, it is included in detail below
Step：
(1), the synthesis of more pi-allyl urethane type addition products：
In the reaction vessel with stirring, 51.1 grams of hydroxy-ethyl acrylate (HEA), 0.011 gram of hydroquinones are sequentially added
With 0.101 gram of tin dilaurate dibutene base tin, stirred under conditions of room temperature, logical nitrogen；Then, 50 grams of diphenyl are added
Methane diisocyanate (MDI), is warming up to 55-65 DEG C, and stirs, and acrylate monomers is occurred with isocyanate-monomer anti-
Should, sampled during the course of the reaction every 1 hour, with the content of determination of infrared spectroscopy isocyano (- NCO), until in system
Untill without isocyano, that is, more pi-allyl urethane type addition products are made, are designated as HEA-MDI.
(2), the mixing of unsaturated polyester (UP)/linked system：
In the reaction vessel with stirring, the unsaturated polyester resin DS988 of 90 grams of O-phthalic acid types is sequentially added, 30
Gram HEA-MDI, 80 grams of HDDA, 3-4 hours are stirred at a temperature of 70-80 DEG C, until DS988/HEA-MDI/HDDA systems are complete
It is well mixed.
(3), the curing molding of the unsaturated polyester resin without styrene：
100 parts of the uniform DS988/HEA-MDI/HDDA resins prepared in step (2) are taken, in room temperature, stirring condition
1.5 parts of cobalt iso-octoates of lower addition and 2.0 parts of methyl ethyl ketone peroxides, and stir；By this containing the DS988/ for triggering system
HEA-MDI/HDDA mixtures import mould, solidify the regular hour under room temperature (about 25 DEG C), you can are made and are free of styrene
Unsaturated polyester resin material, be designated as material B.
Embodiment 3
A kind of preparation method of the unsaturated polyester resin without styrene is present embodiments provided, it is included in detail below
Step：
(1), the synthesis of more pi-allyl urethane type addition products：
In the reaction vessel with stirring, 51.1 grams of hydroxy-ethyl acrylate (HEA), 0.011 gram of hydroquinones are sequentially added
With 0.101 gram of tin dilaurate dibutene base tin, stirred under conditions of room temperature, logical nitrogen；Then, 50 grams of diphenyl are added
Methane diisocyanate (MDI), is warming up to 55-65 DEG C, and stirs, and acrylate monomers is occurred with isocyanate-monomer anti-
Should, sampled during the course of the reaction every 1 hour, with the content of determination of infrared spectroscopy isocyano (- NCO), until in system
Untill without isocyano, that is, more pi-allyl urethane type addition products are made, are designated as HEA-MDI.
(2), the mixing of unsaturated polyester (UP)/linked system：
In the reaction vessel with stirring, the unsaturated polyester resin DS988 of 100 grams of O-phthalic acid types is sequentially added,
20 grams of HEA-MDI, 80 grams of HDDA, 3-4 hours are stirred at a temperature of 70-80 DEG C, until DS988/HEA-MDI/HDDA systems are complete
It is complete well mixed.
(3), the curing molding of the unsaturated polyester resin without styrene：
100 parts of the uniform DS988/HEA-MDI/HDDA resins prepared in step (2) are taken, in room temperature, stirring condition
1.5 parts of cobalt iso-octoates of lower addition and 2.0 parts of methyl ethyl ketone peroxides, and stir；By this containing the DS988/ for triggering system
HEA-MDI/HDDA mixtures import mould, solidify the regular hour under room temperature (about 25 DEG C), you can are made and are free of styrene
Unsaturated polyester resin material, be designated as material C.
Embodiment 4
A kind of preparation method of the unsaturated polyester resin without styrene is present embodiments provided, it is included in detail below
Step：
(1), the synthesis of more pi-allyl urethane type addition products：
In the reaction vessel with stirring, 51.1 grams of hydroxy-ethyl acrylate (HEA), 0.011 gram of hydroquinones are sequentially added
With 0.101 gram of tin dilaurate dibutene base tin, stirred under conditions of room temperature, logical nitrogen；Then, 50 grams of diphenyl are added
Methane diisocyanate (MDI), is warming up to 55-65 DEG C, and stirs, and acrylate monomers is occurred with isocyanate-monomer anti-
Should, sampled during the course of the reaction every 1 hour, with the content of determination of infrared spectroscopy isocyano (- NCO), until in system
Untill without isocyano, that is, more pi-allyl urethane type addition products are made, are designated as HEA-MDI.
(2), the mixing of unsaturated polyester (UP)/linked system：
In the reaction vessel with stirring, the unsaturated polyester resin DS988 of 110 grams of O-phthalic acid types is sequentially added,
40 grams of HEA-MDI, 50 grams of HDDA, 3-4 hours are stirred at a temperature of 70-80 DEG C, until DS988/HEA-MDI/HDDA systems are complete
It is complete well mixed.
(3), the curing molding of the unsaturated polyester resin without styrene：
100 parts of the uniform DS988/HEA-MDI/HDDA resins prepared in step (2) are taken, in room temperature, stirring condition
1.5 parts of cobalt iso-octoates of lower addition and 2.0 parts of cumyl hydroperoxides, and stir；By this containing the DS988/ for triggering system
HEA-MDI/HDDA mixtures import mould, solidify the regular hour under room temperature (about 25 DEG C), you can are made and are free of styrene
Unsaturated polyester resin material, be designated as material D.
Embodiment 5
A kind of preparation method of the unsaturated polyester resin without styrene is present embodiments provided, it is included in detail below
Step：
(1), the synthesis of more pi-allyl urethane type addition products：
In the reaction vessel with stirring, 57.2 grams of hydroxyethyl methacrylate (HEMA), hydroquinones are sequentially added
0.011 gram, 0.107 gram of tin dilaurate dibutene base tin, stirred under conditions of room temperature, logical nitrogen；Then, 50 grams are added
Methyl diphenylene diisocyanate (MDI), is warming up to 55-65 DEG C, and stirs, and makes acrylate monomers and isocyanate-monomer
React, sampled during the course of the reaction every 1 hour, with the content of determination of infrared spectroscopy isocyano (- NCO), until
Untill being free of isocyano in system, that is, more pi-allyl urethane type addition product HEMA-MDI are made.
(2), the mixing of unsaturated polyester (UP)/linked system：
In the reaction vessel with stirring, the unsaturated polyester resin DS988 of 90 grams of O-phthalic acid types is sequentially added, 40
Gram HEMA-MDI, 70 grams of HDDA, 3-4 hours are stirred at a temperature of 70-80 DEG C, until DS988/HEMA-MDI/HDDA systems are complete
It is complete well mixed.
(3), the curing molding of the unsaturated polyester resin without styrene：
100 parts of the uniform DS988/HEMA-MDI/HDDA resins prepared in step (2) are taken, in room temperature, stirring condition
2.0 parts of benzoyl peroxides of lower addition, and stir；By this containing the DS988/HEMA-MDI/HDDA mixing for triggering system
Thing imports mould, solidifies the regular hour at a temperature of about 80 DEG C, you can the unsaturated polyester resin material without styrene is made,
It is designated as material E.
Embodiment 6
A kind of preparation method of the unsaturated polyester resin without styrene is present embodiments provided, it is included in detail below
Step：
(1), the synthesis of more pi-allyl urethane type addition products：
In the reaction vessel with stirring, 57.2 grams of hydroxyethyl methacrylate (HEMA), hydroquinones are sequentially added
0.011 gram, 0.107 gram of tin dilaurate dibutene base tin, stirred under conditions of room temperature, logical nitrogen；Then, 50 grams are added
Methyl diphenylene diisocyanate (MDI), is warming up to 55-65 DEG C, and stirs, and makes acrylate monomers and isocyanate-monomer
React, sampled during the course of the reaction every 1 hour, with the content of determination of infrared spectroscopy isocyano (- NCO), until
Untill being free of isocyano in system, that is, more pi-allyl urethane type addition product HEMA-MDI are made.
(2), the mixing of unsaturated polyester (UP)/linked system：
In the reaction vessel with stirring, the unsaturated polyester resin DS988 of 90 grams of O-phthalic acid types is sequentially added, 40
Gram HEMA-MDI, 70 grams of trimethylolpropane trimethacrylates (TMPTA), 3-4 hours are stirred at a temperature of 70-80 DEG C, until
DS988/HEMA-MDI/TMPTA systems are mixed thoroughly.
(3), the curing molding of the unsaturated polyester resin without styrene：
100 parts of the uniform DS988/HEMA-MDI/TMPTA resins prepared in step (2) are taken, in room temperature, stirring bar
1 part of dimethyl-p-toluidine and 2 parts of benzoyl peroxides are added under part, and is stirred；By this system containing initiation
DS988/HEMA-MDI/TMPTA mixtures import mould, solidify the regular hour at a temperature of room temperature (about 25 DEG C), you can system
The unsaturated polyester resin material without styrene is obtained, is designated as material F.
Embodiment 7
A kind of preparation method of the unsaturated polyester resin without styrene is present embodiments provided, it is included in detail below
Step：
(1), the synthesis of more pi-allyl urethane type addition products：
In the reaction vessel with stirring, 64.4 grams of hydroxyethyl methacrylate (HEMA) is sequentially added, methyl is to benzene two
0.011 gram of phenol, 0.114 gram of stannous octoate, stirred under conditions of room temperature, logical nitrogen；Then, 50 grams of isophorones are added
Diisocyanate (IPDI), is warming up to 55-65 DEG C, and stirs, and acrylate monomers is reacted with isocyanate-monomer,
Sampled during the course of the reaction every 1 hour, with the content of determination of infrared spectroscopy isocyano (- NCO), until being free of in system
Untill isocyano, that is, more pi-allyl urethane type addition product HEMA-IPDI are made.
(2), the mixing of unsaturated polyester (UP)/linked system：
In the reaction vessel with stirring, the unsaturated polyester resin DS988 of 90 grams of O-phthalic acid types is sequentially added, 60
Gram HEMA-IPDI, 50 grams of HDDA, 3-4 hours are stirred at a temperature of 70-80 DEG C, until DS988/HEMA-IPDI/HDDA systems
It is mixed thoroughly.
(3), the curing molding of the unsaturated polyester resin without styrene：
100 parts of the uniform DS988/HEMA-IPDI/HDDA resins prepared in step (2) are taken, in room temperature, stirring bar
1.5 parts of cobalt iso-octoates and 2.0 parts of methyl ethyl ketone peroxides are added under part, and are stirred；By this containing the DS988/ for triggering system
HEMA-IPDI/HDDA mixtures import mould, solidify the regular hour under room temperature (about 25 DEG C), you can are made and are free of benzene second
The unsaturated polyester resin material of alkene, is designated as material G.
Embodiment 8
A kind of preparation method of the unsaturated polyester resin without styrene is present embodiments provided, it is included in detail below
Step：
(1), the synthesis of more pi-allyl urethane type addition products：
In the reaction vessel with stirring, 57.2 grams of hydroxyethyl methacrylate (HEMA), hydroquinones are sequentially added
0.011 gram, 0.107 gram of tin dilaurate dibutene base tin, stirred under conditions of room temperature, logical nitrogen；Then, 50 grams are added
Methyl diphenylene diisocyanate (MDI), is warming up to 55-65 DEG C, and stirs, and makes acrylate monomers and isocyanate-monomer
React, sampled during the course of the reaction every 1 hour, with the content of determination of infrared spectroscopy isocyano (- NCO), until
Untill being free of isocyano in system, that is, more pi-allyl urethane type addition product HEMA-MDI are made.
(2), the mixing of unsaturated polyester (UP)/linked system：
In the reaction vessel with stirring, the unsaturated polyester resin DS988 of 90 grams of O-phthalic acid types is sequentially added, 30
Gram HEMA-MDI, 20 grams of TMPTA, 60 grams of HDDA, 3-4 hours are stirred at a temperature of 70-80 DEG C, until DS988/HEMA-MDI/
TMPTA/HDDA systems are mixed thoroughly.
(3), the curing molding of the unsaturated polyester resin without styrene：
100 parts of the uniform DS988/HEMA-MDI/TMPTA/HDDA resins prepared in step (2) are taken, in room temperature, are stirred
1.5 parts of cobalt iso-octoates and 2.0 parts of methyl ethyl ketone peroxides are added under the conditions of mixing, and are stirred；By this system containing initiation
DS988/HEMA-MDI/TMPTA/HDDA mixtures import mould, solidify the regular hour under room temperature (about 25 DEG C), you can system
The unsaturated polyester resin material of styrene must be free of, is designated as material H.
Test case
Tested respectively according to method as defined in GB/T2567-2008 and obtain materials A-H's prepared by 1-8 of the embodiment of the present invention
Tensile strength, bending strength, impact strength and elongation at break；This is tested respectively according to method as defined in GB/T1634-1989
Materials A-H heat distortion temperature is obtained prepared by inventive embodiments 1-8, specific test result is see as shown in table 1 below.
Table 1
From table 1 it follows that the tensile strength for the unsaturated polyester resin without styrene that the present invention is prepared
For 35-50MPa, bending strength 45-75MPa, impact strength 6-18KJ/m2, it is known that, its processing characteristics and mechanical property with
This area is traditional suitable using the unsaturated polyester resin of Styrene solidification, but the unsaturated polyester (UP) that the application is prepared
Resin has more excellent impact property, and (impact strength for the unsaturated polyester resin that the application obtains is up to 18KJ/m2, and show
The impact strength for having the unsaturated polyester resin containing styrene is generally only 7KJ/m2)。
Above-mentioned detailed description is illustrating for possible embodiments of the present invention, and the embodiment simultaneously is not used to limit this hair
Bright the scope of the claims, all equivalence enforcements or change without departing from carried out by the present invention, it is intended to be limited solely by the scope of the claims of this case.
Claims (10)
1. a kind of preparation method of the unsaturated polyester resin without styrene, it comprises the following steps：
(1), under an inert atmosphere, acrylate monomers, polymerization inhibitor and catalyst are well mixed, obtain compound；Again to
Isocyanate-monomer is added in the compound so that acrylate monomers react with isocyanate-monomer, until in system
Reaction terminates during without isocyano, obtains more pi-allyl urethane type addition products；
Preferably, reaction temperature described in step (1) is 55-65 DEG C；
(2), the unsaturated polyester (UP) without styrene, step (1) more pi-allyl urethane type addition products and acrylic compounds are handed over
Receipts or other documents in duplicate body is well mixed, and obtains unsaturated polyester (UP)/linked system；
It is further preferred that described be well mixed of step (2) is realized by stirring 3-4 hours at 70-80 DEG C；
(3) initiator, is added into step (2) unsaturated polyester (UP)/linked system, after being well mixed, gained is mixed
Compound is solidified, and obtains the unsaturated polyester resin for being free of styrene；
It is further preferred that the solidification temperature is 25-100 DEG C, hardening time 10-30min.
2. preparation method according to claim 1, it is characterised in that the acrylate monomers include acrylic acid hydroxyl second
One or more of combinations in ester, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxy propyl methacrylate；
Preferably, the isocyanate-monomer includes toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, hexa-methylene two
Isocyanate, IPDI, PPDI and one kind or several in 1,4- cyclohexane diisocyanates
The combination of kind.
3. preparation method according to claim 1, it is characterised in that the polymerization inhibitor includes hydroquinones, methyl to benzene
One kind or any two kinds of combination in diphenol, TBHQ；
Preferably, the catalyst is included in tetramethyl butylamine, triethylene diamine, tin dilaurate dibutene base tin and stannous octoate
One or more of combinations.
4. according to the preparation method described in claim any one of 1-3, it is characterised in that the acrylate monomers and isocyanide
The dosage of acid ester monomer respectively in terms of hydroxyl and isocyano, wherein, the mol ratio of hydroxyl and isocyano is 1.03-1.1；
Counted using the gross mass of acrylate monomers and isocyanate-monomer as 100%, the dosage of the polymerization inhibitor is 0.005-
0.1%, the dosage of catalyst is 0.05-0.5%.
5. preparation method according to claim 1, it is characterised in that unsaturated polyester (UP) used includes adjacent benzene in step (2)
One kind or several in diformazan acid type unsaturated polyester (UP), M-phthalic acid type unsaturated polyester (UP) and terephthaldehyde's acid type unsaturated polyester (UP)
The combination of kind；
Preferably, the acrylic cross-linking monomer includes the propylene of hexylene glycol two, tripropylene glycol diacrylate, diethyl two
One or more of groups in alcohol diacrylate, trimethylolpropane trimethacrylate, TEGDMA
Close；
It is further preferred that counted using the gross mass of unsaturated polyester (UP)/linked system as 100%, in the unsaturated polyester (UP)/crosslinking
In components system, the mass percent of unsaturated polyester (UP) is 40-70%, and the mass percent of more pi-allyl urethane type addition products is
5-30%, the mass percent of acrylic cross-linking monomer is 20-50%.
6. preparation method according to claim 1, it is characterised in that the initiator includes methyl ethyl ketone peroxide, peroxide
Change cyclohexanone, benzoyl peroxide, dilauroyl peroxide, isopropyl benzene hydroperoxide, azodiisobutyronitrile, ABVN,
One or more of combinations in the benzoyl peroxide tert-butyl ester and double (4- tert-butylcyclohexyls) peroxy dicarbonates；
Preferably, counted using the gross weight number of the unsaturated polyester (UP)/linked mixture as 100, the use of the initiator
Measure as 0.1-4.0 parts by weight.
7. preparation method according to claim 1, it is characterised in that step (3) adds promotion also into the mixture
Agent；
Preferably, the accelerator includes cobalt iso-octoate, cobalt naphthenate, manganese naphthenate, vanadium iso-octoate, dimethylaniline, diethyl
One kind or any two kinds of combination in base aniline and dimethyl-p-toluidine；
It is highly preferred that counted using the gross weight number of the unsaturated polyester (UP)/linked mixture as 100, the accelerator
Dosage is 0.1-2.0 parts by weight.
8. the preparation method of the unsaturated polyester resin without styrene described in claim any one of 1-7 is prepared not
Unsaturated polyester resin containing styrene；
Preferably, the tensile strength of the unsaturated polyester resin is 35-50MPa, bending strength 45-75MPa, and impact strength is
6-18KJ/m2, heat distortion temperature is 40-55 DEG C, elongation at break 2.5-6.0%.
9. application of the unsaturated polyester resin without styrene in Polyester button is prepared described in claim 8.
10. a kind of Polyester button, it is prepared as the unsaturated polyester resin without styrene described in claim 8
's.
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| CN111690098A (en) * | 2020-05-29 | 2020-09-22 | 华南理工大学 | Room temperature solidified styrene-free unsaturated polyester resin material and preparation method thereof |
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