CN107298738A - A kind of low temperature resistant unsaturated polyester resin compositions and preparation method thereof - Google Patents
A kind of low temperature resistant unsaturated polyester resin compositions and preparation method thereof Download PDFInfo
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- CN107298738A CN107298738A CN201710533220.4A CN201710533220A CN107298738A CN 107298738 A CN107298738 A CN 107298738A CN 201710533220 A CN201710533220 A CN 201710533220A CN 107298738 A CN107298738 A CN 107298738A
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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Abstract
A kind of low temperature resistant unsaturated polyester resin compositions, in parts by weight, its preparing raw material includes：46 52 parts of maleic anhydride, 112 128 parts of straight chained alkyl glycol, 29 38 parts of M-phthalic acid, 22 29 parts of itaconic acid, 1,268 parts of propane diols, 33 42 parts of triethylene glycol, 30 38 parts of 3,4 thiophene dicarboxylic acid, 46 57 parts of styrene, 19 25 parts of 2 vinyl thiophene.
Description
Technical field
The present invention relates to field of polymer technology, and in particular to a kind of low temperature resistant unsaturated polyester resin compositions and its preparation side
Method.
Background technology
In recent years, with fast-developing, synthesis cost gradually reduction, the raising of quality of materials, synthesis of science and technology
Resin turns into one of demand in the world and the maximum material of yield.The application field of synthetic resin is constantly widened, and in agricultural, is built
Build, the field such as automobile and electronics play the role of it is important.Unsaturated polyester resin is important industry in Resin Industry, with matter
Amount is light, high intensity, premium properties such as workability etc., is easily used for preparing the complicated product of various large scale structures, is that one kind has very
The versatile material of big superiority.The domestic demand for unsaturated polyester resin is to be in that the state supplied, insatiable hunger need to be more than at present
Production and processing industry with polyester grow up therewith.In countries such as Japan, North Americas, unsaturated polyester resin industrial development is fast
Speed, and have huge market.
Unsaturated polyester resin (UPR) is by saturation dihydric alcohol and unsaturated dibasic acid, unsaturated dicarboxylic acid anhydride dehydration contracting
The fluoropolymer resin closed.Long chain is presented in usual resinous molecular structure, and structure has the insatiable hunger of special non-aromatic in containing
And carbon-carbon double bond, the thermosetting plastics of crosslinking net macromolecular structure is reacted under crosslinking agent and initiator effect.Polymerization
The property of thing is species and the chain structure that is formed by used monomer to determine.
The synthesis material of unsaturated polyester (UP) includes unsaturated dibasic acid class and alcohols.Contain unsaturation in unsaturated dibasic acid
Carbon-carbon double bond.In unsaturated polyester (UP) preparation process, unsaturated carbon can be introduced for resin by participating in the unsaturated dibasic acid of reaction
Carbon double bond.The proportioning of unsaturated dibasic acid is higher, and the content of the unsaturated double-bond contained in its molecule will be higher, crosslinking degree
Will be higher, the heat distortion temperature after solidification because of resin will be higher.And the structure of binary acid also can produce one to polymer
Fixed influence.
Reacted in maleic anhydride molecular structure in the form of acid anhydrides with alcohol, more other binary acid were reacting
A molecular water is generated in journey less.But maleic anhydride with alcohol during reacting, isomerization is easily produced, the tree finally given
Resin difference prepared by the structure and fumaric acid of fat is simultaneously little.
Fumaric acid acid anhydride, be otherwise known as fumaric acid anhydride, is the transisomer of maleic anhydride.The easy molecule of transconfiguration
Between more well-regulated arrangement.Because the resin using fumaric acid as Material synthesis is than Resin crystallization prepared by maleic acid
The stronger, softening point of property is higher.It is more more stable than cis maleic anhydride, and fusing point is higher.
Alcohols reacts to form long-chain polymer with unsaturated dibasic acid.Usually using the alcohols energy of molecular chain length or line style
Improve the flexibility of polymer.The alcohols being commonly used has ethylene glycol, diethylene glycol, 1,2- propane diols, neopentyl glycol, a contracting diethyl
Glycol and polyalcohol etc..
Ethylene glycol is simplest one kind of structure in di-alcohols.Ethylene glycol is due to having symmetry in structure so that poly-
The resin closed has preferable crystallinity.Fumaric acid is exactly a kind of easily precipitation with the unsaturated polyester (UP) that ethylene glycol synthesizes
The resin of crystal.And the intermiscibility between ethylene glycol and styrene is poor, often it is used in mixed way with other alcohols.
Diethylene glycol can effectively improve the mechanical property of product.If as carried aromatic ring structure in alcohol, so that it may be made firm
The polymer of property structure, and the water imbibition of product can be effectively reduced.
1,2-PD has stronger activity, can be with many binary acid reactive polymeric resins.Simultaneously because price
Cheap, 1,2-PD is a kind of more conventional dihydric alcohol.
Neopentyl glycol molecular structure is a kind of linear structure, with good symmetry.Because it has symmetrical structure, newly
Pentanediol has preferable crystallinity.The resin that neopentyl glycol reacts generation with fumaric acid has crystallinity.And the alcohol is favourable
In the alkali resistance and water resistance that improve synthetic resin, it is difficult occur hydrolysis with hydrone.But neopentyl glycol and styrene
Poor compatibility, need to be used in mixed way with other alcohols in use.
The linear structure of diglycol molecular structure, and strand is longer in small molecular alcohol.Prepared as raw material
Unsaturated polyester resin have preferable flexible, the crystallinity of resin can be reduced.But it is more due to existing in the resin
Oxygen bridge, resin has stronger sensitiveness to water.Compatibility between this alcohol and styrene is not so good as propane diols.
Polyalcohol is exactly containing the alcohol micromolecular for having more than 2 hydroxy functional groups in molecule.During using this alcohols as raw material
Side chain is easily produced, network structure is formed.Therefore the mechanical property of this resin is good.But it is due to easily production in the course of the polymerization process
Raw side chain, molecule is wound and viscosity increase between causing prepolymer, and premature gelation is difficult to control reaction process.
Unsaturated polyester (UP) has good mechanical property, electrical property and a chemical-resistance, and raw material be easy to get it is low with price
Honest and clean, its composite is widely used in the industry such as ship, automobile, building materials industry.But UPR solidfied material generally there are poor toughness, strong
Degree is not high, easy cracking, the shortcomings of shrinkage factor is big, so as to limit its application.
The content of the invention
In order to solve prior art problem, the first aspect of the present invention provides a kind of low temperature resistant unsaturated polyester resin combination
Thing, in parts by weight, its preparing raw material include：46-52 parts of maleic anhydride, 112-128 parts of straight chained alkyl glycol, M-phthalic acid
29-38 parts, 22-29 parts of itaconic acid, 6-8 parts of 1,2- propane diols, 33-42 parts of triethylene glycol, 30-38 parts of 3,4- thiophene dicarboxylic acids, benzene
46-57 parts of ethene, 19-25 parts of 2- vinyl thiophenes.
In some embodiments, low temperature resistant unsaturated polyester resin compositions as described above, in parts by weight, it is made
Standby raw material includes：49 parts of maleic anhydride, 120 parts of straight chained alkyl glycol, 33.2 parts of M-phthalic acid, 26 parts of itaconic acid, 1,2- third
7.6 parts of glycol, 37.5 parts of triethylene glycol, 34.4 parts of 3,4- thiophene dicarboxylic acids, 52 parts of styrene, 22 parts of 2- vinyl thiophenes.
In some embodiments, the straight chained alkyl glycol contains 4-12 carbon atom.
In some embodiments, the straight chained alkyl glycol contains 8-10 carbon atom.
In some embodiments, the straight chained alkyl glycol is nonanediol.
In some embodiments, the mol ratio of the styrene and 2- vinyl thiophenes is 5：2.
In some embodiments, the mol ratio of the 2- vinyl thiophenes and 3,4- thiophene dicarboxylic acid are 1：1.
The second aspect of the present invention provides a kind of preparation method of low temperature resistant unsaturated polyester resin compositions, including as follows
Step：The air in reactor is excluded with High Purity Nitrogen, 6-8 parts of 1,2-PD, 33-42 parts of triethylene glycol, maleic anhydride 46- is added
52 parts, it is warming up to 80 DEG C, stirs 30min, then add 29-38 part of M-phthalic acid, then be warming up to 145 DEG C, stirs 1h, then plus
Enter 112-128 parts of straight chained alkyl glycol, be warming up to 210 DEG C, stir 1h, add 30-38 parts of 3,4- thiophene dicarboxylic acids and clothing health
It is sour 22-29 parts, 4h is stirred, 160 DEG C are cooled to, 19-25 parts of 2- vinyl thiophenes is added, stirs, continue to be cooled to 95 DEG C,
46-57 parts of styrene is added, room temperature is cooled to, produces.
In some embodiments, the preparation method of low temperature resistant unsaturated polyester resin compositions, comprises the following steps：With
High Purity Nitrogen excludes the air in reactor, adds 7.6 parts of 1,2-PD, 37.5 parts of triethylene glycol, 49 parts of maleic anhydride, is warming up to
80 DEG C, 30min is stirred, 33.2 parts of M-phthalic acid is then added, then is warming up to 145 DEG C, 1h is stirred, adds straight chained alkyl two
120 parts of alcohol, is warming up to 210 DEG C, stirs 1h, adds 26 parts of 34.4 parts of 3,4- thiophene dicarboxylic acids and itaconic acid, stirs 4h, cooling
To 160 DEG C, 22 parts of 2- vinyl thiophenes are added, are stirred, continued to be cooled to 95 DEG C, add 52 parts of styrene, be cooled to room
Temperature, is produced.
The third aspect of the present invention provides a kind of curing of low temperature resistant unsaturated polyester resin compositions, to low temperature resistant
0.5wt% organic peroxide is added in unsaturated polyester resin compositions, stirs, adds 0.01wt% isooctyl acids
Cobalt, is molded in a mold.
The fourth aspect of the present invention provides a kind of low temperature resistant unsaturated polyester resin compositions in auto industry, aircraft system
Make, radar manufacture, ship, the application in field of chemical equipment.
Embodiment
The participation in the election detailed description of the invention below for being preferable to carry out method and including embodiment this hair can be more easily understood
Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with art of the present invention
The identical implication that technical staff is generally understood that.When there is contradiction, the definition in this specification is defined.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements
Thing, step, method, product or device are not necessarily limited to those key elements, but can include not expressly listed other key elements or
Such a composition, step, method, product or the intrinsic key element of device.
Conjunction " Consists of " excludes any key element do not pointed out, step or component.If be used in claim, this
Phrase will make claim be closed, it is not included the material in addition to materials of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following in the clause that phrase " Consists of " appears in claim main body after theme,
It is only limited to the key element described in the clause；Other key elements are not excluded outside as the overall claim.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value is limited, this, which is appreciated that, specifically discloses by any range limit or preferred value and any scope
All scopes that any pairing of lower limit or preferred value is formed, regardless of whether whether the scope separately discloses.For example, when open
During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When number range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end
Value and all integers and fraction within the range.
Singulative includes plural number and object is discussed, unless the context clearly dictates otherwise." optional " or it is " any
It is a kind of " refer to that the item or event that describe thereafter may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, represents that the present invention is not limited to this specific
Quantity, includes the part of the amendment of the acceptable change without cause related basic function close to the quantity.Phase
Answer, modify a numerical value with " about ", " about " etc., mean that the invention is not restricted to the exact numerical.In some examples, approximately
Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, scope is limited can be with
Combine and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.
In addition, the indefinite article " one kind " and " one " before key element of the present invention or component are to key element or the quantitative requirement of component
(i.e. occurrence number) unrestriction.Therefore " one " or " one kind " should be read as including one or at least one, and odd number
The key element or component of form also include plural form, unless the obvious purport of the quantity refers to singulative.
The first aspect of the present invention provides a kind of low temperature resistant unsaturated polyester resin compositions, in parts by weight, and it is prepared
Raw material includes：46-52 parts of maleic anhydride, 112-128 parts of straight chained alkyl glycol, 29-38 parts of M-phthalic acid, itaconic acid 22-29
Part, 6-8 parts of 1,2- propane diols, 33-42 parts of triethylene glycol, 30-38 parts of 3,4- thiophene dicarboxylic acids, 46-57 parts of styrene, 2- vinyl
19-25 parts of thiophene.
In some embodiments, low temperature resistant unsaturated polyester resin compositions as described above, in parts by weight, it is made
Standby raw material includes：49 parts of maleic anhydride, 120 parts of straight chained alkyl glycol, 33.2 parts of M-phthalic acid, 26 parts of itaconic acid, 1,2- third
7.6 parts of glycol, 37.5 parts of triethylene glycol, 34.4 parts of 3,4- thiophene dicarboxylic acids, 52 parts of styrene, 22 parts of 2- vinyl thiophenes.
In some embodiments, the straight chained alkyl glycol contains 4-12 carbon atom.
In some embodiments, the straight chained alkyl glycol contains 8-10 carbon atom.
In some embodiments, the straight chained alkyl glycol is nonanediol.
In some embodiments, the mol ratio of the styrene and 2- vinyl thiophenes is 5：2.
In some embodiments, the mol ratio of the 2- vinyl thiophenes and 3,4- thiophene dicarboxylic acid are 1：1.
Maleic anhydride, CAS accession number 108-31-6, also known as maleic anhydride (MAH), abbreviation cis-butenedioic anhydride, are maleics two
The acid anhydrides of acid, is at room temperature sour colourless or white solid, molecular formula is C4H2O3.
The instantiation of straight chained alkyl glycol includes, BDO, 1,5-PD, 1,6- hexylene glycols, 1,7- heptan two
Alcohol, 1,8- ethohexadiols, 1,9- nonanediols, 1,10- decanediols, the glycol of 1,11- 11, the glycol of 1,12- 12.
Some preferred embodiment in, the straight chained alkyl glycol be 1,8- ethohexadiols, 1,9- nonanediols, 1,10-
Decanediol.
In some preferred embodiments, the straight chained alkyl glycol is 1,9- nonanediols.
1,9- nonanediol, CAS accession number 3937-56-2 are a kind of important organic diols, a kind of purposes is wider to be had
Machine raw material, is basic material in organic synthesis industry；It can be additionally used in production lubricant, plasticizer simultaneously；It can also be used for medicine
In terms of；Available for liquid crystal material, degradable function high polymer material；Spices, lubricating oil, ink, coating, cosmetics, plasticising
The production of agent and various additives etc..It can be additionally used in the synthesis of a variety of organic intermediates.
M-phthalic acid, CAS accession number 121-91-5, also referred to as isophathalic acid, 1,3- phthalic acids.It is a kind of white crystalline
Powder or acicular crystal.Alcohol and glacial acetic acid are soluble in, boiling water is slightly soluble in but insoluble in cold water, is practically insoluble in benzene and petroleum ether.
Itaconic acid, CAS accession number 97-65-4, also referred to as methene butanedioic acid, methylene-succinic acid are that unsaturated binary is organic
Acid.It contains unsaturated double-bond, with active chemical property, can carry out the polymerization between itself, also can be with other monomers such as propylene
Nitrile etc. polymerize, and is dissolved in water, other solvents such as ethanol；Various addition reactions, esterification and polymerisation can be carried out, is chemical conjunction
It is also the important source material of Chemical Manufacture into the important source material of industry.
1,2-PD, CAS 57-55-6, with water, ethanol and a variety of immiscible organic solvents, its chemical formula is C3H8O2.
It is colourless viscous liquid under normality, it is almost tasteless, carefully hear micro- sweet tea.Propane diols can be used as the raw material of unsaturated polyester resin.Changing
It can coordinate in cosmetic, toothpaste and perfumed soap with glycerine or sorbierite and be used as wetting agent.It is used as damping, even hair agent in hair dye,
As antifreezing agent, glassine paper, plasticizer and pharmaceuticals industry are additionally operable to.
Triethylene glycol, CAS 112-27-6.3,4- thiophene dicarboxylic acids, CAS 4282-29-5.Styrene, CAS accession number
100-42-5.2- vinyl thiophenes, CAS accession number 1918-82-7.
Inventor is had found under study for action, and the toughness of unsaturated polyester resin can be adjusted using straight chained alkyl glycol, is introduced
3,4- thiophene dicarboxylic acids can increase the intensity of unsaturated polyester resin, intensity particularly at low temperature, also have at -20 DEG C
There is good intensity.Interaction between thiophene on sulphur also causes packing of molecules to more crosslinking points are introduced in system
It is closer, the space in three-dimensional netted macromolecular is smaller.2- vinyl thiophenes are added to styrene according to a certain percentage
In, shrinkage factor can be adjusted while the low temperature intensity of resin is ensured.Expand the application of unsaturated polyester resin.
The second aspect of the present invention provides a kind of preparation method of low temperature resistant unsaturated polyester resin compositions, including as follows
Step：The air in reactor is excluded with High Purity Nitrogen, 6-8 parts of 1,2-PD, 33-42 parts of triethylene glycol, maleic anhydride 46- is added
52 parts, it is warming up to 80 DEG C, stirs 30min, then add 29-38 part of M-phthalic acid, then be warming up to 145 DEG C, stirs 1h, then plus
Enter 112-128 parts of straight chained alkyl glycol, be warming up to 210 DEG C, stir 1h, add 30-38 parts of 3,4- thiophene dicarboxylic acids and clothing health
It is sour 22-29 parts, 4h is stirred, 160 DEG C are cooled to, 19-25 parts of 2- vinyl thiophenes is added, stirs, continue to be cooled to 95 DEG C,
46-57 parts of styrene is added, room temperature is cooled to, produces.
In some embodiments, the preparation method of low temperature resistant unsaturated polyester resin compositions, comprises the following steps：With
High Purity Nitrogen excludes the air in reactor, adds 7.6 parts of 1,2-PD, 37.5 parts of triethylene glycol, 49 parts of maleic anhydride, is warming up to
80 DEG C, 30min is stirred, 33.2 parts of M-phthalic acid is then added, then is warming up to 145 DEG C, 1h is stirred, adds straight chained alkyl two
120 parts of alcohol, is warming up to 210 DEG C, stirs 1h, adds 26 parts of 34.4 parts of 3,4- thiophene dicarboxylic acids and itaconic acid, stirs 4h, cooling
To 160 DEG C, 22 parts of 2- vinyl thiophenes are added, are stirred, continued to be cooled to 95 DEG C, add 52 parts of styrene, be cooled to room
Temperature, is produced.
The acid value that existing synthetic method is obtained is 20-50mg/g, and the synthetic method that the present invention is provided can allow respectively
Individual component is fully reacted, and the acid number of composition is 10-15mg/g.
Acid number for neutralize 1g unsaturated polyester (UP) compositions required for KOH milligram number.
The assay method of acid number is：
1. taking 1g phenolphthalein to be mixed with 99g ethanol is made into indicator；
2. toluene and ethanol are taken with volume ratio 1：1 is made into mixed solvent；
3. weighing 5.6gKOH to be dissolved in 1L distilled water, 0.1g o-2 potassium acid hydrogen potassium is then taken to calibrate mole of KOH solution
Concentration, adds indicator；
4. taking 1g unsaturated polyester resin compositions in 250mL conical flasks, mixed solvent is taken with 20mL pipettes respectively
Be added in the conical flask containing unsaturated polyester resin compositions and blank conical flask in；
5. 3 drop indicator are added separately in the conical flask containing unsaturated polyester resin compositions and blank taper
In bottle, titrated with KOH solution, the volume of record consumption KOH solution, Unit/mL obtains molten containing unsaturated polyester resin compositions
Liquid and blank solution are designated as V and V0 respectively；
6. acid number calculation formula：
M is the quality of unsaturated polyester resin compositions, g；The KOH milligram numbers that V is consumed by sample；V0 is blank sample
The KOH milligram numbers consumed；N is the molar concentration of KOH solution, mol/L.
The third aspect of the present invention provides a kind of curing of low temperature resistant unsaturated polyester resin compositions, to low temperature resistant
0.5wt% organic peroxide is added in unsaturated polyester resin compositions, stirs, adds 0.01wt% isooctyl acids
Cobalt, is molded in a mold.
The fourth aspect of the present invention provides a kind of low temperature resistant unsaturated polyester resin compositions in auto industry, aircraft system
Make, radar manufacture, ship, the application in field of chemical equipment.
The present invention is expanded on further with reference to specific embodiment.
Embodiment 1
A kind of low temperature resistant unsaturated polyester resin compositions, in parts by weight, its preparing raw material includes：Maleic anhydride 49
Part, 120 parts of 1,9- nonanediols, 33.2 parts of M-phthalic acid, 26 parts of itaconic acid, 7.6 parts of 1,2- propane diols, 37.5 parts of triethylene glycol,
34.4 parts of 3,4- thiophene dicarboxylic acids, 52 parts of styrene, 22 parts of 2- vinyl thiophenes.
Preparation method：With High Purity Nitrogen exclude reactor in air, add 7.6 parts of 1,2-PD, 37.5 parts of triethylene glycol,
49 parts of maleic anhydride, is warming up to 80 DEG C, stirs 30min, then adds 33.2 parts of M-phthalic acid, then be warming up to 145 DEG C, stirring
1h, adds 120 parts of 1,9- nonanediols, is warming up to 210 DEG C, stirs 1h, adds 34.4 parts of 3,4- thiophene dicarboxylic acids and clothing health
26 parts of acid, stirs 4h, is cooled to 160 DEG C, adds 22 parts of 2- vinyl thiophenes, stirs, and continues to be cooled to 95 DEG C, adds benzene
52 parts of ethene, is cooled to room temperature, produces.Acid number 12mg/g.
Curing：The 0.5wt% of composition weight peroxide is added into low temperature resistant unsaturated polyester resin compositions
Change cyclohexanone, stir, add the 0.01wt% cobalt iso-octoates of composition weight, be molded in a mold.
Embodiment 2
A kind of low temperature resistant unsaturated polyester resin compositions, in parts by weight, its preparing raw material includes：Maleic anhydride 49
Part, 120 parts of 1,8- ethohexadiols, 33.2 parts of M-phthalic acid, 26 parts of itaconic acid, 7.6 parts of 1,2- propane diols, 37.5 parts of triethylene glycol,
34.4 parts of 3,4- thiophene dicarboxylic acids, 52 parts of styrene, 22 parts of 2- vinyl thiophenes.
Preparation method：With High Purity Nitrogen exclude reactor in air, add 7.6 parts of 1,2-PD, 37.5 parts of triethylene glycol,
49 parts of maleic anhydride, is warming up to 80 DEG C, stirs 30min, then adds 33.2 parts of M-phthalic acid, then be warming up to 145 DEG C, stirring
1h, adds 120 parts of 1,8- ethohexadiols, is warming up to 210 DEG C, stirs 1h, adds 34.4 parts of 3,4- thiophene dicarboxylic acids and clothing health
26 parts of acid, stirs 4h, is cooled to 160 DEG C, adds 22 parts of 2- vinyl thiophenes, stirs, and continues to be cooled to 95 DEG C, adds benzene
52 parts of ethene, is cooled to room temperature, produces.Acid number 14mg/g.
Curing：The 0.5wt% of composition weight peroxide is added into low temperature resistant unsaturated polyester resin compositions
Change cyclohexanone, stir, add the 0.01wt% cobalt iso-octoates of composition weight, be molded in a mold.
Embodiment 3
A kind of low temperature resistant unsaturated polyester resin compositions, in parts by weight, its preparing raw material includes：Maleic anhydride 49
Part, 120 parts of 1,10- decanediols, 33.2 parts of M-phthalic acid, 26 parts of itaconic acid, 7.6 parts of 1,2- propane diols, 37.5 parts of triethylene glycol,
34.4 parts of 3,4- thiophene dicarboxylic acids, 52 parts of styrene, 22 parts of 2- vinyl thiophenes.
Preparation method：With High Purity Nitrogen exclude reactor in air, add 7.6 parts of 1,2-PD, 37.5 parts of triethylene glycol,
49 parts of maleic anhydride, is warming up to 80 DEG C, stirs 30min, then adds 33.2 parts of M-phthalic acid, then be warming up to 145 DEG C, stirring
1h, adds 120 parts of 1,10- decanediols, is warming up to 210 DEG C, stirs 1h, adds 34.4 parts of 3,4- thiophene dicarboxylic acids and clothing health
26 parts of acid, stirs 4h, is cooled to 160 DEG C, adds 22 parts of 2- vinyl thiophenes, stirs, and continues to be cooled to 95 DEG C, adds benzene
52 parts of ethene, is cooled to room temperature, produces.Acid number 15mg/g.
Curing：The 0.5wt% of composition weight peroxide is added into low temperature resistant unsaturated polyester resin compositions
Change cyclohexanone, stir, add the 0.01wt% cobalt iso-octoates of composition weight, be molded in a mold.
Comparative example 1
A kind of low temperature resistant unsaturated polyester resin compositions, in parts by weight, its preparing raw material includes：Maleic anhydride 49
Part, 120 parts of 1,9- nonanediols, 33.2 parts of M-phthalic acid, 26 parts of itaconic acid, 7.6 parts of 1,2- propane diols, 37.5 parts of triethylene glycol,
52 parts of styrene, 22 parts of 2- vinyl thiophenes.
Preparation method：With High Purity Nitrogen exclude reactor in air, add 7.6 parts of 1,2-PD, 37.5 parts of triethylene glycol,
49 parts of maleic anhydride, is warming up to 80 DEG C, stirs 30min, then adds 33.2 parts of M-phthalic acid, then be warming up to 145 DEG C, stirring
1h, adds 120 parts of 1,9- nonanediols, is warming up to 210 DEG C, stirs 1h, adds 26 parts of itaconic acid, stirs 4h, is cooled to 160
DEG C, 22 parts of 2- vinyl thiophenes are added, are stirred, continues to be cooled to 95 DEG C, adds 52 parts of styrene, be cooled to room temperature, i.e.,
.Acid number 36mg/g.
Curing：The 0.5wt% of composition weight peroxide is added into low temperature resistant unsaturated polyester resin compositions
Change cyclohexanone, stir, add the 0.01wt% cobalt iso-octoates of composition weight, be molded in a mold.
Comparative example 2
A kind of low temperature resistant unsaturated polyester resin compositions, in parts by weight, its preparing raw material includes：Maleic anhydride 49
Part, 120 parts of 1,9- nonanediols, 33.2 parts of M-phthalic acid, 26 parts of itaconic acid, 7.6 parts of 1,2- propane diols, 37.5 parts of triethylene glycol,
34.4 parts of 3,4- thiophene dicarboxylic acids, 52 parts of styrene.
Preparation method：With High Purity Nitrogen exclude reactor in air, add 7.6 parts of 1,2-PD, 37.5 parts of triethylene glycol,
49 parts of maleic anhydride, is warming up to 80 DEG C, stirs 30min, then adds 33.2 parts of M-phthalic acid, then be warming up to 145 DEG C, stirring
1h, adds 120 parts of 1,9- nonanediols, is warming up to 210 DEG C, stirs 1h, adds 34.4 parts of 3,4- thiophene dicarboxylic acids and clothing health
26 parts of acid, stirs 4h, is cooled to 95 DEG C, adds 52 parts of styrene, is cooled to room temperature, produces.Acid number 42mg/g.
Curing：The 0.5wt% of composition weight peroxide is added into low temperature resistant unsaturated polyester resin compositions
Change cyclohexanone, stir, add the 0.01wt% cobalt iso-octoates of composition weight, be molded in a mold.
Comparative example 3
A kind of low temperature resistant unsaturated polyester resin compositions, in parts by weight, its preparing raw material includes：Maleic anhydride 49
Part, 120 parts of 1,9- nonanediols, 33.2 parts of M-phthalic acid, 26 parts of itaconic acid, 7.6 parts of 1,2- propane diols, 37.5 parts of triethylene glycol,
52 parts of styrene.
Preparation method：With High Purity Nitrogen exclude reactor in air, add 7.6 parts of 1,2-PD, 37.5 parts of triethylene glycol,
49 parts of maleic anhydride, is warming up to 80 DEG C, stirs 30min, then adds 33.2 parts of M-phthalic acid, then be warming up to 145 DEG C, stirring
1h, adds 120 parts of 1,9- nonanediols, is warming up to 210 DEG C, stirs 1h, adds 26 parts of itaconic acid, stirs 4h, is cooled to 95
DEG C, 52 parts of styrene is added, room temperature is cooled to, produces.Acid number 55mg/g.
Curing：The 0.5wt% of composition weight peroxide is added into low temperature resistant unsaturated polyester resin compositions
Change cyclohexanone, stir, add the 0.01wt% cobalt iso-octoates of composition weight, be molded in a mold.
Method of testing
1. shock-testing
According to GB/T 11548, tested using XJL-300B tubing drop hammer impact testing machines.By embodiment 1-3 and right
Sample after ratio 1-3 solidifications pre-processes 2h when -15 DEG C and -20 DEG C；Drop hammer tup diameter 90mm, and quality of dropping hammer is 10kg,
Record shock height, unit mm.
2. shrinkage factor is tested
Densimetry in ISO3521 determines embodiment 1-3 and comparative example 1-3 shrinkage factor.
Test result is listed in the table below.
It is described above, it is only the present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto, and is appointed
What those familiar with the art is the invention discloses in the range of, technique according to the invention scheme and inventive concept
It is subject to equivalent substitution or change, belongs to protection scope of the present invention.
Claims (10)
1. a kind of low temperature resistant unsaturated polyester resin compositions, it is characterised in that in parts by weight, its preparing raw material includes：Horse
Carry out 46-52 parts of acid anhydrides, 112-128 parts of straight chained alkyl glycol, 29-38 parts of M-phthalic acid, 22-29 parts of itaconic acid, 1,2- the third two
6-8 parts of alcohol, 33-42 parts of triethylene glycol, 30-38 parts of 3,4- thiophene dicarboxylic acids, 46-57 parts of styrene, 2- vinyl thiophenes 19-25
Part.
2. low temperature resistant unsaturated polyester resin compositions as claimed in claim 1, it is characterised in that in parts by weight, it is made
Standby raw material includes：49 parts of maleic anhydride, 120 parts of straight chained alkyl glycol, 33.2 parts of M-phthalic acid, 26 parts of itaconic acid, 1,2- third
7.6 parts of glycol, 37.5 parts of triethylene glycol, 34.4 parts of 3,4- thiophene dicarboxylic acids, 52 parts of styrene, 22 parts of 2- vinyl thiophenes.
3. low temperature resistant unsaturated polyester resin compositions as claimed in claim 1, it is characterised in that the straight chained alkyl glycol
Contain 8-10 carbon atom.
4. low temperature resistant unsaturated polyester resin compositions as claimed in claim 1, it is characterised in that the straight chained alkyl glycol
For nonanediol.
5. low temperature resistant unsaturated polyester resin compositions as claimed in claim 1, it is characterised in that the styrene and 2- second
The mol ratio of alkenyl thiophene is 5：2.
6. low temperature resistant unsaturated polyester resin compositions as claimed in claim 1, it is characterised in that the 2- vinyl thiophenes
Mol ratio with 3,4- thiophene dicarboxylic acids is 1：1.
7. the preparation side of the low temperature resistant unsaturated polyester resin compositions as described in any one of claim 1-6 claim
Method, it is characterised in that comprise the following steps：The air in reactor is excluded with High Purity Nitrogen, 6-8 parts of 1,2-PD, three are added
33-42 parts of glycol, 46-52 parts of maleic anhydride, are warming up to 80 DEG C, stir 30min, then add 29-38 parts of M-phthalic acid, then
145 DEG C are warming up to, 1h is stirred, adds 112-128 parts of straight chained alkyl glycol, 210 DEG C are warming up to, 1h is stirred, adds 3,4-
22-29 parts of 30-38 parts of thiophene dicarboxylic acid and itaconic acid, stir 4h, are cooled to 160 DEG C, add 19-25 parts of 2- vinyl thiophenes,
Stir, continue to be cooled to 95 DEG C, add 46-57 parts of styrene, be cooled to room temperature, produce.
8. the preparation side of the low temperature resistant unsaturated polyester resin compositions as described in any one of claim 1-6 claim
Method, it is characterised in that comprise the following steps：The air in reactor is excluded with High Purity Nitrogen, 7.6 parts of 1,2-PD, three are added
37.5 parts of glycol, 49 parts of maleic anhydride, are warming up to 80 DEG C, stir 30min, then add 33.2 parts of M-phthalic acid, then heat up
To 145 DEG C, 1h is stirred, 120 parts of straight chained alkyl glycol is added, be warming up to 210 DEG C, stirred 1h, add 3,4- thiophene dicarboxyls
26 parts of 34.4 parts of acid and itaconic acid, stir 4h, are cooled to 160 DEG C, add 22 parts of 2- vinyl thiophenes, stir, and continue cold
But to 95 DEG C, 52 parts of styrene is added, room temperature is cooled to, produces.
9. the solidification side of the low temperature resistant unsaturated polyester resin compositions as described in any one of claim 1-6 claim
Method, it is characterised in that 0.5wt% organic peroxide is added into low temperature resistant unsaturated polyester resin compositions, stirring is equal
It is even, 0.01wt% cobalt iso-octoates are added, are molded in a mold.
10. the low temperature resistant unsaturated polyester resin compositions as described in any one of claim 1-6 claim are in automobile work
Application in industry, aircraft manufacturing, radar manufacture, ship, field of chemical equipment.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101137694A (en) * | 2005-01-18 | 2008-03-05 | 亚什兰许可和知识产权有限公司 | Low viscosity unsaturated polyester resin with reduced voc emission levels |
| CN101602849A (en) * | 2009-07-09 | 2009-12-16 | 湖南大学 | Dimer acid modified unsaturated polyester resin and synthetic method thereof |
| CN101735405A (en) * | 2009-12-29 | 2010-06-16 | 浙江天和树脂有限公司 | Imitation marble unsaturated polyester resin and preparation method thereof |
| CN106280196A (en) * | 2016-08-27 | 2017-01-04 | 安徽省新力复合材料有限公司 | A kind of heat resistant unsaturated polyester resin |
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2017
- 2017-07-03 CN CN201710533220.4A patent/CN107298738B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101137694A (en) * | 2005-01-18 | 2008-03-05 | 亚什兰许可和知识产权有限公司 | Low viscosity unsaturated polyester resin with reduced voc emission levels |
| CN101602849A (en) * | 2009-07-09 | 2009-12-16 | 湖南大学 | Dimer acid modified unsaturated polyester resin and synthetic method thereof |
| CN101735405A (en) * | 2009-12-29 | 2010-06-16 | 浙江天和树脂有限公司 | Imitation marble unsaturated polyester resin and preparation method thereof |
| CN106280196A (en) * | 2016-08-27 | 2017-01-04 | 安徽省新力复合材料有限公司 | A kind of heat resistant unsaturated polyester resin |
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