CN107663264B - A kind of unsaturated polyester resin and the preparation method and application thereof without styrene - Google Patents
A kind of unsaturated polyester resin and the preparation method and application thereof without styrene Download PDFInfo
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- CN107663264B CN107663264B CN201710858285.6A CN201710858285A CN107663264B CN 107663264 B CN107663264 B CN 107663264B CN 201710858285 A CN201710858285 A CN 201710858285A CN 107663264 B CN107663264 B CN 107663264B
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- unsaturated polyester
- preparation
- styrene
- monomer
- polyester resin
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Classifications
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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
-
- 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
Abstract
The present invention provides a kind of unsaturated polyester resin and the preparation method and application thereof without styrene.The preparation method includes under an inert atmosphere, acrylate monomers, polymerization inhibitor and catalyst being uniformly mixed, mixture is obtained；Isocyanate-monomer is added into the mixture again so that acrylate monomers react with isocyanate-monomer, reacting when until being free of isocyano in system terminates, and obtains polyenoid propyl urethane type addition product；Unsaturated polyester (UP), the polyenoid propyl urethane type addition product and acrylic cross-linking monomer without styrene are uniformly mixed, unsaturated polyester (UP)/cross-linking component system is obtained；Initiator is added into the system again, after mixing, 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 comparable processing performance and mechanical property therewith, and has superior impact property.
Description
Technical field
The present invention relates to a kind of unsaturated polyester resin and the preparation method and application thereof without styrene, it is auxiliary to belong to clothes
Material material and its preparation technical field.
Background technique
Currently, Polyester button used in this field is using unsaturated polyester resin as primary raw material, it is to hand over styrene
Join curing component and diluent, additive appropriate is added, gel is carried out in particular device and mold, curing molding is pearly-lustre
Or the plate or bar of non-pearly-lustre, then it is manufactured through a series of machining and surface treatment.Wherein, unsaturated polyester tree
The button of rouge production has the characteristics that acid and alkali-resistance and high temperature resistant laundering, and color is full of variety, and physicochemical property is excellent, is widely applied
It is the leading products of clothes button in dress accessory.
During using unsaturated polyester (UP) for main material production thermosetting polyester button, the dosage of styrene reaches
30%, it is even higher.And the vapour pressure of styrene at room temperature is higher, readily volatilized, and has irritating special odor,
To eyes and the irritating effect of upper respiratory tract mucosa, therefore its volatility and toxic side effect will necessarily be good for environment and operator
Health causes great harm.
It is used as cross-linking component and the diluent institute of unsaturated polyester (UP) in order to reduce or even eliminate current this field for styrene
Caused negative effect needs to select or design the crosslinking list of the unsaturated polyester (UP) small with synthesis volatility and toxic side effect
Body, to replace traditional styrene, so that the material of Polyester button and preparation process have environmental-friendly characteristic, thus significantly
Ground improves the working environment of manufacturing enterprise and operator, ensures their health；Meanwhile eliminating the volatilization and residual of styrene
The adverse effect that ecological environment is generated.
Therefore, harm caused by styrene how is eliminated, working condition is improved, has protected the health of environment and operator
Manufacturing enterprise as Polyester button manufacturing enterprise or even thermosetting property unsaturated polyester material faced one is urgently to be resolved
Problem.
Summary of the invention
In order to solve the above shortcomings and deficiencies, it is poly- that the purpose of the present invention is to provide a kind of unsaturations without styrene
The preparation method of ester resin.
The object of the invention is also to provide the unsaturated polyester (UP)s prepared by the preparation method without styrene
Resin.
The object of the invention is also to provide the above-mentioned unsaturated polyester resins without styrene in preparing Polyester button
Application.
It is the unsaturated polyester (UP) tree by above-mentioned without styrene the object of the invention is also to provide a kind of Polyester button
What rouge was prepared.
In order to achieve the above objectives, the present invention provides a kind of preparation method of unsaturated polyester resin without styrene,
The following steps are included:
(1), under an inert atmosphere, acrylate monomers, polymerization inhibitor and catalyst are uniformly mixed, obtain mixture；
Isocyanate-monomer is added into the mixture again so that acrylate monomers react with isocyanate-monomer, until body
Reaction terminates when being free of isocyano in system, obtains polyenoid propyl urethane type addition product；
(2), unsaturated polyester (UP), step (1) the polyenoid propyl urethane type addition product and the acrylic acid of styrene will be free of
Class cross-linking monomer is uniformly mixed, and obtains unsaturated polyester (UP)/cross-linking component system；
(3), initiator is added into step (2) unsaturated polyester (UP)/cross-linking component system, after mixing, by institute
It obtains mixture to be solidified, obtains the unsaturated polyester resin for being free of styrene.
Specific embodiment according to the present invention, step (1) is described to be uniformly mixed to realize by stirring at room temperature, this
Outside, it is also required to be stirred after isocyanate-monomer being added, wherein used stir is this field routine techniques in step (1)
Means.
Specific embodiment according to the present invention the measurement of isocyano and its contains in the preparation method, in step (1)
The judgement of amount every 1 hour specifically includes the following steps: during the reaction, sampled, measurement (using infrared spectrometer) isocyanide
The content of acid group (- NCO), until being free of isocyano in system.
Specific embodiment according to the present invention, step (3) described initiator is added under room temperature, stirring condition, is added
It can be made to be uniformly mixed with unsaturated polyester (UP)/cross-linking component system by continuing stirring after entering；
In addition, step (3) described solidification can carry out in the traditional dies of this field.
Specific embodiment according to the present invention, in the preparation method, it is preferable that the acrylate monomers packet
Include hydroxy-ethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), hydroxypropyl acrylate (HPA) and methacrylic acid hydroxypropyl
The combination of one or more of ester (HPMA).If the acrylate monomers include combination several in above-mentioned substance,
They can be used in mixed way with arbitrary proportion.
Specific embodiment according to the present invention, in the preparation method, it is preferable that the isocyanate-monomer includes
Toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), hexa-methylene diisocyanate vinegar (HDI), different Fo Er
The combination of one or more of ketone diisocyanate (IPDI), paraphenylene diisocyanate and 1,4- cyclohexane diisocyanate.
If the isocyanate-monomer includes combination several in above-mentioned substance, they can be used in mixed way with arbitrary proportion.
Specific embodiment according to the present invention, in the preparation method, it is preferable that the polymerization inhibitor includes to benzene two
One of phenol, methyl hydroquinone, tert-butyl hydroquinone or any two kinds of combination.If the polymerization inhibitor includes above-mentioned object
Two kinds of combination in matter, then they can be used in mixed way with arbitrary proportion.
Specific embodiment according to the present invention, in the preparation method, it is preferable that the catalyst includes tetramethyl
The combination of one or more of 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.
Specific embodiment according to the present invention, in the preparation method, it is preferable that the acrylate monomers and
The dosage of isocyanate-monomer is respectively in terms of hydroxyl (- OH) and isocyano (- NCO), wherein mole of hydroxyl and isocyano
Than for 1.03-1.1；
It is in terms of 100% by the gross mass of acrylate monomers and isocyanate-monomer, the dosage of the polymerization inhibitor is
0.005-0.1%, the dosage of catalyst are 0.05-0.5%.
Specific embodiment according to the present invention, in the preparation method, it is preferable that temperature is reacted described in step (1)
Degree is 55-65 DEG C.
Specific embodiment according to the present invention, in the 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)
One or more of combination.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 field may be incorporated for originally using conventional substances, any synthesis or the commercially available product
Invention.
Specific embodiment according to the present invention, in the preparation method, it is preferable that the acrylic cross-linking monomer
Including two acrylic ester of hexylene glycol (HDDA), tripropylene glycol diacrylate (TPGDA), diethylene glycol diacrylate
(DEGDA), one of trimethylolpropane trimethacrylate (TMPTA), triethylene glycol dimethacrylate (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.
Specific embodiment according to the present invention, in the preparation method, it is preferable that with unsaturated polyester (UP)/crosslinking group
The gross mass of fission system is 100% meter, in the unsaturated polyester (UP)/cross-linking component system, the quality percentage of unsaturated polyester (UP)
Number is 40-70%, and the mass percent of polyenoid propyl urethane type addition product is 5-30%, the quality hundred of acrylic cross-linking monomer
Score is 20-50%.
Specific embodiment according to the present invention, in the preparation method, it is preferable that step (2) is described to be uniformly mixed
It is to be realized by stirring 3-4 hours at 70-80 DEG C.
Specific embodiment according to the present invention, in the preparation method, it is preferable that the initiator includes peroxidating
Methyl ethyl ketone (MEKP), cyclohexanone peroxide, benzoyl peroxide (BPO), dilauroyl peroxide (LPO), isopropyl benzene hydroperoxide
(CHP), azodiisobutyronitrile (AIBN), azobisisoheptonitrile (ABVN), benzoyl peroxide (TBPB) and bis- (uncles 4-
Butylcyclohexyl) one or more of peroxy dicarbonate combination.If the initiator includes several in above-mentioned substance
Combination, then they can be used in mixed way with arbitrary proportion.
Specific embodiment according to the present invention, in the preparation method, it is preferable that with the unsaturated polyester (UP)/friendship
The total weight number for joining component mixture is 100 meters, and the dosage of the initiator is 0.1-4.0 parts by weight.
Specific embodiment according to the present invention, in the preparation method, it is preferable that the solidification temperature is 25-100
DEG C, curing time 10-30min.
Specific embodiment according to the present invention, in the preparation method, it is preferable that step (3) is also to the mixing
Promotor is added in object.
Specific embodiment according to the present invention, in the preparation method, it is preferable that the promotor includes isooctyl acid
One of cobalt, cobalt naphthenate, manganese naphthenate, vanadium iso-octoate, dimethylaniline, diethylaniline and dimethyl-p-toluidine or
Any two kinds of combination.If the promotor includes combination several in above-mentioned substance, they can be mixed with arbitrary proportion makes
With.
Specific embodiment according to the present invention, in the preparation method, it is preferable that with the unsaturated polyester (UP)/friendship
The total weight number for joining component mixture is 100 meters, and the dosage of the promotor is 0.1-2.0 parts by weight.
It is prepared not the present invention also provides the preparation method by the above-mentioned unsaturated polyester resin without styrene
Unsaturated polyester resin containing styrene.
Specific embodiment according to the present invention, it is preferable that should be without the tensile strength of 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%.
The present invention also provides the above-mentioned unsaturated polyester resins without styrene to prepare the application in Polyester button.
It the present invention also provides a kind of Polyester button, is prepared by the unsaturated polyester resin without styrene
It arrives.
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, to pass through a kind of new type functional for reacting synthesis of acrylate monomers and isocyanate-monomer
Reactive polyenoid propyl urethane type addition product is that the first cross-linking component will be certain with acrylate monomer for the second cross-linking component
The unsaturated polyester (UP) of ratio/polyenoid propyl urethane type addition product/acrylate monomer is mixed under certain condition
Resin system；Suitable initiator and promotor is added into the hybrid resin system again, it is then solid at a proper temperature
Chemical conversion type, so that the unsaturated polyester resin material without styrene be made.
It can be seen that preparation method provided by the present invention does not use the cross-linking component benzene of traditional unsaturated polyester (UP) completely
Ethylene does not need the preparation process for significantly adjusting or changing unsaturated polyester resin yet, available with synthesis by selecting, designing
The novel cross-linking component for making unsaturated polyester (UP), successfully has developed the unsaturated polyester resin without styrene.And the system
Preparation Method is a kind of method for not using styrene environmental-friendly completely, the preparation method can improve significantly manufacturing enterprise and
The working environment of operator ensures their health；Meanwhile the volatilization that can also eliminate styrene and residual are to ecological ring
The adverse effect that border generates.
Specifically, not with the unsaturated polyester resin of the Styrene solidification of this field routine and general low-styrene
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 polyenoid propyl ammonia
Ester type addition product and acrylic ester monomer are the cross-linking component and diluent of unsaturated polyester (UP), completely instead of styrene, system
It is standby gone out the excellent unsaturated polyester resin without styrene of physical mechanical property, improve unsaturated polyester resin material or
The production environment of the manufacturing enterprise of product eliminates the volatilization of styrene to the health of worker and the negative effect of ecological environment；
(2) in the preparation method, it can be used as the new type functional reactivity polyenoid third of the cross-linking component 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
It uses, 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 comparable processing performance and a mechanical property therewith, and it is with superior 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 defined
Polyester resin is tested for the property, and measuring its tensile strength is 35-50MPa, bending strength 45-75MPa, impact strength 6-
18KJ/m2, elongation at break 2.5-6.0%；This, which is tested, according to the method for GB/T1634-1989 defined 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.
Detailed description of the invention
Fig. 1 is raw materials used hydroxy-ethyl acrylate (HEA), methyl diphenylene diisocyanate in the embodiment of the present invention 1
(MDI) and the infared spectrum of preparation-obtained polyenoid propyl urethane type addition product (HEA-MDI).
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now in conjunction in detail below
Embodiment carries out following detailed description to technical solution of the present invention, but should not be understood as the limit to enforceable range of the invention
It is fixed.
Embodiment 1
Present embodiments provide a kind of preparation method of unsaturated polyester resin without styrene comprising in detail below
Step:
(1), the synthesis of polyenoid propyl urethane type addition product:
In the reaction vessel (conventional reactor that this field uses) with stirring, hydroxy-ethyl acrylate is sequentially added
(HEA) 51.1 grams, 0.101 gram of 0.011 gram of hydroquinone and tin dilaurate dibutene base tin, under conditions of room temperature, logical nitrogen
It stirs evenly；Then, 50 grams of methyl diphenylene diisocyanates (MDI) are added, is warming up to 55-65 DEG C, and stir, makes hydroxyl third
Acrylic monomer reacts with isocyanate-monomer, samples during the reaction every 1 hour, with determination of infrared spectroscopy isocyanide
The content of acid group (- NCO) obtains polyenoid propyl urethane type addition product, is denoted as until being free of isocyano in system
HEA-MDI。
Wherein, polyenoid propyl urethane type adduct HEA-MDI made from the present embodiment and 2 kinds of raw materials of the adduct are synthesized
The infared spectrum of HEA and MDI is as shown in Figure 1, from figure 1 it appears that the characteristic absorption peak of isocyanate group is located in MDI
2274cm-1, but with the progress of reaction, the characteristic peak at this is gradually decrease to disappear, this shows that isocyanate group disappears completely
Consumption, it is possible to determine that synthesized the set goal product HEA-MDI.
(2), unsaturated polyester (UP)/cross-linking component system mixing:
In the reaction vessel (conventional reactor that this field 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
Enester (HDDA) stirs 3-4 hours at a temperature of 70-80 DEG C, until DS988/HEA-MDI/HDDA system is mixed thoroughly.
(3), the curing molding of the unsaturated polyester resin without styrene:
Prepared 100 parts of uniform DS988/HEA-MDI/HDDA resin in step (2) is 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 evenly；By this containing the DS988/ for causing system
HEA-MDI/HDDA mixture imports mold, solidifies the regular hour under room temperature (about 25 DEG C), can be prepared by without styrene
Unsaturated polyester resin material, be denoted as materials A.
Embodiment 2
Present embodiments provide a kind of preparation method of unsaturated polyester resin without styrene comprising in detail below
Step:
(1), the synthesis of polyenoid propyl urethane type addition product:
In the reaction vessel with stirring, 51.1 grams of hydroxy-ethyl acrylate (HEA) is sequentially added, 0.011 gram of hydroquinone
With 0.101 gram of tin of tin dilaurate dibutene base, stirred evenly 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 stir, and acrylate monomers and isocyanate-monomer occurs anti-
It answers, was sampled during the reaction every 1 hour, with the content of determination of infrared spectroscopy isocyano (- NCO), until in system
Until without isocyano, polyenoid propyl urethane type addition product is obtained, HEA-MDI is denoted as.
(2), unsaturated polyester (UP)/cross-linking component system mixing:
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, are stirred 3-4 hours at a temperature of 70-80 DEG C, until DS988/HEA-MDI/HDDA system is complete
It is uniformly mixed.
(3), the curing molding of the unsaturated polyester resin without styrene:
Prepared 100 parts of uniform DS988/HEA-MDI/HDDA resin in step (2) is 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 evenly；By this containing the DS988/ for causing system
HEA-MDI/HDDA mixture imports mold, solidifies the regular hour under room temperature (about 25 DEG C), can be prepared by without styrene
Unsaturated polyester resin material, be denoted as material B.
Embodiment 3
Present embodiments provide a kind of preparation method of unsaturated polyester resin without styrene comprising in detail below
Step:
(1), the synthesis of polyenoid propyl urethane type addition product:
In the reaction vessel with stirring, 51.1 grams of hydroxy-ethyl acrylate (HEA) is sequentially added, 0.011 gram of hydroquinone
With 0.101 gram of tin of tin dilaurate dibutene base, stirred evenly 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 stir, and acrylate monomers and isocyanate-monomer occurs anti-
It answers, was sampled during the reaction every 1 hour, with the content of determination of infrared spectroscopy isocyano (- NCO), until in system
Until without isocyano, polyenoid propyl urethane type addition product is obtained, HEA-MDI is denoted as.
(2), unsaturated polyester (UP)/cross-linking component system mixing:
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 are stirred 3-4 hours at a temperature of 70-80 DEG C, until DS988/HEA-MDI/HDDA system is complete
It is complete to be uniformly mixed.
(3), the curing molding of the unsaturated polyester resin without styrene:
Prepared 100 parts of uniform DS988/HEA-MDI/HDDA resin in step (2) is 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 evenly；By this containing the DS988/ for causing system
HEA-MDI/HDDA mixture imports mold, solidifies the regular hour under room temperature (about 25 DEG C), can be prepared by without styrene
Unsaturated polyester resin material, be denoted as material C.
Embodiment 4
Present embodiments provide a kind of preparation method of unsaturated polyester resin without styrene comprising in detail below
Step:
(1), the synthesis of polyenoid propyl urethane type addition product:
In the reaction vessel with stirring, 51.1 grams of hydroxy-ethyl acrylate (HEA) is sequentially added, 0.011 gram of hydroquinone
With 0.101 gram of tin of tin dilaurate dibutene base, stirred evenly 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 stir, and acrylate monomers and isocyanate-monomer occurs anti-
It answers, was sampled during the reaction every 1 hour, with the content of determination of infrared spectroscopy isocyano (- NCO), until in system
Until without isocyano, polyenoid propyl urethane type addition product is obtained, HEA-MDI is denoted as.
(2), unsaturated polyester (UP)/cross-linking component system mixing:
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 are stirred 3-4 hours at a temperature of 70-80 DEG C, until DS988/HEA-MDI/HDDA system is complete
It is complete to be uniformly mixed.
(3), the curing molding of the unsaturated polyester resin without styrene:
Prepared 100 parts of uniform DS988/HEA-MDI/HDDA resin in step (2) is 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 evenly；By this containing the DS988/ for causing system
HEA-MDI/HDDA mixture imports mold, solidifies the regular hour under room temperature (about 25 DEG C), can be prepared by without styrene
Unsaturated polyester resin material, be denoted as material D.
Embodiment 5
Present embodiments provide a kind of preparation method of unsaturated polyester resin without styrene comprising in detail below
Step:
(1), the synthesis of polyenoid propyl urethane type addition product:
In the reaction vessel with stirring, 57.2 grams of hydroxyethyl methacrylate (HEMA), hydroquinone are sequentially added
It 0.011 gram, 0.107 gram of tin of tin dilaurate dibutene base, is stirred evenly 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 stir, makes acrylate monomers and isocyanate-monomer
It reacts, was sampled during the reaction every 1 hour, with the content of determination of infrared spectroscopy isocyano (- NCO), until
Without until isocyano in system, polyenoid propyl urethane type addition product HEMA-MDI is obtained.
(2), unsaturated polyester (UP)/cross-linking component system mixing:
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, are stirred 3-4 hours at a temperature of 70-80 DEG C, until DS988/HEMA-MDI/HDDA system is complete
It is complete to be uniformly mixed.
(3), the curing molding of the unsaturated polyester resin without styrene:
Prepared 100 parts of uniform DS988/HEMA-MDI/HDDA resin in step (2) is taken, in room temperature, stirring condition
2.0 parts of benzoyl peroxides of lower addition, and stir evenly；This is mixed containing the DS988/HEMA-MDI/HDDA for causing system
Object imports mold, solidifies the regular hour at a temperature of about 80 DEG C, can be prepared by the unsaturated polyester resin material of no styrene,
It is denoted as material E.
Embodiment 6
Present embodiments provide a kind of preparation method of unsaturated polyester resin without styrene comprising in detail below
Step:
(1), the synthesis of polyenoid propyl urethane type addition product:
In the reaction vessel with stirring, 57.2 grams of hydroxyethyl methacrylate (HEMA), hydroquinone are sequentially added
It 0.011 gram, 0.107 gram of tin of tin dilaurate dibutene base, is stirred evenly 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 stir, makes acrylate monomers and isocyanate-monomer
It reacts, was sampled during the reaction every 1 hour, with the content of determination of infrared spectroscopy isocyano (- NCO), until
Without until isocyano in system, polyenoid propyl urethane type addition product HEMA-MDI is obtained.
(2), unsaturated polyester (UP)/cross-linking component system mixing:
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) are stirred 3-4 hours at a temperature of 70-80 DEG C, until
DS988/HEMA-MDI/TMPTA system is mixed thoroughly.
(3), the curing molding of the unsaturated polyester resin without styrene:
Prepared 100 parts of uniform DS988/HEMA-MDI/TMPTA resin in step (2) is taken, in room temperature, stirring bar
1 part of dimethyl-p-toluidine and 2 parts of benzoyl peroxides are added under part, and stirs evenly；By this system containing initiation
DS988/HEMA-MDI/TMPTA mixture imports mold, solidifies the regular hour at a temperature of room temperature (about 25 DEG C), can make
The unsaturated polyester resin material without styrene is obtained, material F is denoted as.
Embodiment 7
Present embodiments provide a kind of preparation method of unsaturated polyester resin without styrene comprising in detail below
Step:
(1), the synthesis of polyenoid propyl urethane type addition product:
In the reaction vessel with stirring, 64.4 grams of hydroxyethyl methacrylate (HEMA) is sequentially added, methyl is to benzene two
It 0.011 gram of phenol, 0.114 gram of stannous octoate, is stirred evenly 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 stir, acrylate monomers is made to react with isocyanate-monomer,
It was sampled during the reaction every 1 hour, with the content of determination of infrared spectroscopy isocyano (- NCO), until being free of in system
Until isocyano, polyenoid propyl urethane type addition product HEMA-IPDI is obtained.
(2), unsaturated polyester (UP)/cross-linking component system mixing:
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, are stirred 3-4 hours at a temperature of 70-80 DEG C, until DS988/HEMA-IPDI/HDDA system
It is mixed thoroughly.
(3), the curing molding of the unsaturated polyester resin without styrene:
Prepared 100 parts of uniform DS988/HEMA-IPDI/HDDA resin in step (2) is 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 stir evenly；By this containing the DS988/ for causing system
HEMA-IPDI/HDDA mixture imports mold, solidifies the regular hour under room temperature (about 25 DEG C), can be prepared by without benzene second
The unsaturated polyester resin material of alkene, is denoted as material G.
Embodiment 8
Present embodiments provide a kind of preparation method of unsaturated polyester resin without styrene comprising in detail below
Step:
(1), the synthesis of polyenoid propyl urethane type addition product:
In the reaction vessel with stirring, 57.2 grams of hydroxyethyl methacrylate (HEMA), hydroquinone are sequentially added
It 0.011 gram, 0.107 gram of tin of tin dilaurate dibutene base, is stirred evenly 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 stir, makes acrylate monomers and isocyanate-monomer
It reacts, was sampled during the reaction every 1 hour, with the content of determination of infrared spectroscopy isocyano (- NCO), until
Without until isocyano in system, polyenoid propyl urethane type addition product HEMA-MDI is obtained.
(2), unsaturated polyester (UP)/cross-linking component system mixing:
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, are stirred 3-4 hours at a temperature of 70-80 DEG C, until DS988/HEMA-MDI/
TMPTA/HDDA system is mixed thoroughly.
(3), the curing molding of the unsaturated polyester resin without styrene:
Prepared 100 parts of uniform DS988/HEMA-MDI/TMPTA/HDDA resin in step (2) is taken, in room temperature, is 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 stir evenly；By this system containing initiation
DS988/HEMA-MDI/TMPTA/HDDA mixture imports mold, solidifies the regular hour under room temperature (about 25 DEG C), can make
The unsaturated polyester resin material without styrene is obtained, material H is denoted as.
Test case
It is tested respectively according to method as defined in GB/T2567-2008 and obtains 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
The heat distortion temperature of materials A-H 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, processing performance and mechanical property with
This field is traditional suitable using the unsaturated polyester resin of Styrene solidification, but the unsaturated polyester (UP) that the application is prepared
Resin has superior impact property, and (impact strength for the unsaturated polyester resin that the application obtains is up to 18KJ/m2, and show
There is the impact strength of the unsaturated polyester resin containing styrene to be generally only 7KJ/m2)。
Above-mentioned detailed description is illustrating for possible embodiments of the present invention, and the embodiment is not to limit this hair
Bright the scope of the patents, all equivalence enforcements or change without departing from carried out by the present invention, is intended to be limited solely by the scope of the patents of this case.
Claims (24)
1. a kind of preparation method of the unsaturated polyester resin without styrene comprising following steps:
(1), under an inert atmosphere, acrylate monomers, polymerization inhibitor and catalyst are uniformly mixed, obtain mixture；Again to
Isocyanate-monomer is added in the mixture so that acrylate monomers react with isocyanate-monomer, until in system
Reaction terminates when without isocyano, obtains polyenoid propyl urethane type addition product；
(2), unsaturated polyester (UP), step (1) the polyenoid propyl urethane type addition product and acrylic compounds without styrene are handed over
Receipts or other documents in duplicate body is uniformly mixed, and obtains unsaturated polyester (UP)/cross-linking component system；
(3), initiator is added into step (2) unsaturated polyester (UP)/cross-linking component system, after mixing, gained is mixed
It closes object to be solidified, obtains the unsaturated polyester resin for being free of styrene.
2. preparation method according to claim 1, which is characterized in that the acrylate monomers include acrylic acid hydroxyl second
The combination of one or more of ester, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxy propyl methacrylate.
3. preparation method according to claim 1 or 2, which is characterized in that the isocyanate-monomer includes that toluene two is different
Cyanate, methyl diphenylene diisocyanate, hexa-methylene diisocyanate vinegar, isophorone diisocyanate, to two isocyanide of benzene
The combination of one or more of acid esters and 1,4- cyclohexane diisocyanate.
4. preparation method according to claim 1, which is characterized in that the polymerization inhibitor includes hydroquinone, methyl to benzene
One of diphenol, tert-butyl hydroquinone or any two kinds of combination.
5. preparation method according to claim 1 or 4, which is characterized in that the catalyst includes tetramethyl butylamine, three second
The combination of one or more of alkene diamines, tin dilaurate dibutene base tin and stannous octoate.
6. preparation method according to claim 1, which is characterized in that reaction temperature described in step (1) is 55-65 DEG C.
7. -2,4,6 described in any item preparation methods according to claim 1, which is characterized in that the acrylate monomers and
The dosage of isocyanate-monomer is respectively in terms of hydroxyl and isocyano, wherein the molar ratio of hydroxyl and isocyano is 1.03-
1.1；
It is in terms of 100% by the gross mass of acrylate monomers and isocyanate-monomer, the dosage of the polymerization inhibitor is 0.005-
0.1%, the dosage of catalyst is 0.05-0.5%.
8. preparation method according to claim 3, which is characterized in that the acrylate monomers and isocyanate-monomer
Dosage respectively in terms of hydroxyl and isocyano, wherein the molar ratio of hydroxyl and isocyano is 1.03-1.1；
It is in terms of 100% by the gross mass of acrylate monomers and isocyanate-monomer, the dosage of the polymerization inhibitor is 0.005-
0.1%, the dosage of catalyst is 0.05-0.5%.
9. preparation method according to claim 5, which is characterized in that the acrylate monomers and isocyanate-monomer
Dosage respectively in terms of hydroxyl and isocyano, wherein the molar ratio of hydroxyl and isocyano is 1.03-1.1；
It is in terms of 100% by the gross mass of acrylate monomers and isocyanate-monomer, the dosage of the polymerization inhibitor is 0.005-
0.1%, the dosage of catalyst is 0.05-0.5%.
10. preparation method according to claim 1, which is characterized in that described be uniformly mixed of step (2) is by 70-
Realization in 3-4 hours is stirred at 80 DEG C.
11. preparation method according to claim 1, which is characterized in that unsaturated polyester (UP) used includes adjacent benzene in step (2)
One of diformazan acid type unsaturated polyester (UP), M-phthalic acid type unsaturated polyester (UP) and terephthaldehyde's acid type unsaturated polyester (UP) are several
The combination of kind.
12. according to claim 1 or preparation method described in 11, which is characterized in that the acrylic cross-linking monomer includes for oneself
Two acrylic ester of glycol, tripropylene glycol diacrylate, diethylene glycol diacrylate, trimethylolpropane trimethacrylate,
The combination of one or more of triethylene glycol dimethacrylate.
13. according to claim 1 or preparation method described in 11, which is characterized in that with unsaturated polyester (UP)/cross-linking component system
Gross mass is 100% meter, and in the unsaturated polyester (UP)/cross-linking component system, the mass percent of unsaturated polyester (UP) is 40-
70%, the mass percent of polyenoid propyl urethane type addition product is 5-30%, and the mass percent of acrylic cross-linking monomer is
20-50%.
14. preparation method according to claim 12, which is characterized in that total with unsaturated polyester (UP)/cross-linking component system
Quality is 100% meter, and in the unsaturated polyester (UP)/cross-linking component system, the mass percent of unsaturated polyester (UP) is 40-
70%, the mass percent of polyenoid propyl urethane type addition product is 5-30%, and the mass percent of acrylic cross-linking monomer is
20-50%.
15. preparation method according to claim 1, which is characterized in that the initiator includes methyl ethyl ketone peroxide, peroxide
Change cyclohexanone, benzoyl peroxide, dilauroyl peroxide, isopropyl benzene hydroperoxide, azodiisobutyronitrile, azobisisoheptonitrile,
The combination of one or more of benzoyl peroxide and bis- (4- tert-butylcyclohexyl) peroxy dicarbonates.
16. according to claim 1 or preparation method described in 15, which is characterized in that mixed with the unsaturated polyester (UP)/cross-linking component
The total weight number for closing object is 100 meters, and the dosage of the initiator is 0.1-4.0 parts by weight.
17. preparation method according to claim 1, which is characterized in that promotion is added in step (3) also into the mixture
Agent.
18. preparation method according to claim 17, which is characterized in that the promotor includes cobalt iso-octoate, aphthenic acids
One of cobalt, manganese naphthenate, vanadium iso-octoate, dimethylaniline, diethylaniline and dimethyl-p-toluidine are two kinds any
Combination.
19. preparation method described in 7 or 18 according to claim 1, which is characterized in that with the unsaturated polyester (UP)/cross-linking component
The total weight number of mixture is 100 meters, and the dosage of the promotor is 0.1-2.0 parts by weight.
20. preparation method according to claim 1, which is characterized in that the solidification temperature is 25-100 DEG C, curing time
For 10-30min.
What 21. the preparation method of the described in any item unsaturated polyester resins without styrene of claim 1-20 was prepared
Unsaturated polyester resin without styrene.
22. the unsaturated polyester resin according to claim 21 without styrene, which is characterized in that the unsaturated polyester (UP)
The tensile strength of resin is 35-50MPa, bending strength 45-75MPa, impact strength 6-18KJ/m2, heat distortion temperature is
40-55 DEG C, elongation at break 2.5-6.0%；
Wherein, the tensile strength, bending strength, impact strength and elongation at break are advised according to GBT2567-2008
What fixed method measured；
The heat distortion temperature is measured according to the method for GB/T1634-1989 defined.
23. the unsaturated polyester resin described in claim 21 or 22 without styrene is preparing the application in Polyester button.
24. a kind of Polyester button is prepared by the unsaturated polyester resin as described in claim 21 or 22 without styrene
It obtains.
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