CN107189028A - A kind of preparation method of environment-friendly and high-performance fast demoulding polyurethane reaction injection moulding composition and its self-catalysis chain extender - Google Patents
A kind of preparation method of environment-friendly and high-performance fast demoulding polyurethane reaction injection moulding composition and its self-catalysis chain extender Download PDFInfo
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
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- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
- C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
- C08G18/2027—Heterocyclic amines; Salts thereof containing one heterocyclic ring having two nitrogen atoms in the ring
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- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- C08G18/3271—Hydroxyamines
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- C08G18/40—High-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
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- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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Abstract
The invention discloses the preparation method of a kind of environment-friendly and high-performance fast demoulding polyurethane reaction injection moulding composition and its self-catalysis chain extender.Composition includes two components, and component A includes 1%~10% self-catalysis chain extender and 0.01%~2% composite catalyst, and the self-catalysis chain extender refers to the material with following structure：X=2~5, R is C in formulayH2y+1, y=0~2；The composite catalyst is 10 parts of isooctyl acid bismuth, 1~2 part of isooctyl acid potassium, bicyclic 15 parts of amidine compound, 10 parts of glycerine.B component：MDI 60%~95%, modifying agent 5%~40%, NCO content 23%~28%, the modifying agent includes at least one dihydric alcohol and at least one trihydroxylic alcohol.The preparation method of self-catalysis chain extender is that Piperazine anhydrous are heated into 65 ± 5 DEG C, one kind in oxirane, expoxy propane or epoxy butane is slowly added dropwise into reaction vessel according to mol ratio under temperature constant state, completion of dropping is warming up to 80~85 DEG C of reaction 4h, cooling discharging.Said composition smell is low, VOC is low, good weatherability, demoulding time are short.
Description
Technical field
The present invention relates to polyurethane reaction injecting forming material and preparation technology.
Background technology
The application of polyurethane reaction injection moulding (PU-RIM) material in the car is quite varied, is distinguished from application site
Mainly divide inside gadget and exterior trimming parts.Material in automobile cabin belongs to inside gadget, such as automobile seat foams, such product
Extremely strict are required to environmental-protecting performance such as oder levels, volatile organic matter content etc. of material；In the portion driven out of my cabin
Part is automobile exterior trimming parts, such as skylight, big encirclement, then requires more harsh, the requirement of environmental-protecting performance to material photooxidation aging property
It is then relatively low.But the continuous renewal replacement with product and the continuous improvement to product requirement, many products are all to material
Weatherability and environmental-protecting performance propose dual high request, wherein more typical is exactly automobile glass encapsulation PU-RIM materials
Material, the material had both belonged to exterior trimming parts, it is necessary to higher weatherability, simultaneously because being directly connected with driving cabin, to environmental-protecting performance
It is required that also increasingly improving.Therefore, on the premise of high reaction activity, high-weatherability is ensured, reduction volatile organic matter content,
Smell is reduced, is the subject matter that current this kind of material faces.
Polyurethane material can be divided into aromatic series and the major class of aliphatic two, aromatic series isocyanide according to the difference of isocyanates used
Acid esters is as traditional urethane raw, using relatively broad and deep.But due to containing in the structure of aromatic isocyanate
Phenyl ring, easily reacts and xanthochromia in the presence of illumination；And aliphatic isocyanates have excellent light aging resisting property, but
Aliphatic isocyanates reactivity is relatively low, it is difficult to meet requirements of the PU-RIM to gel and demoulding time.
Patent document CN1633454A, CN1455791A, CN1946756A, CN101061154A, CN101906200 are related to
And the technology of polyurethane material is produced using autocatalytic polyols, but be both needed to coordinate other amines catalysts, technology application
Belong to polyurethane foam material, its reaction speed, molecular structure are unsuitable for reaction and injection molding process；Other foregoing invention institute
The polyalcohol viscosity being related to is larger, and mobility, mold filling character are poor, it is necessary to coordinate a large amount of foaming agents or water to use, also can not be direct
Applied in non-foamed system.
Patent document CN103172822A discloses a kind of fast demoulding weather resistant polyurethane reaction injection moulding combination
Thing and preparation method thereof.The invention can be significantly improved reaction rate, be greatly shortened by using organic metal composite catalyst
Gel and demoulding time, gel time are 8~20s, and demoulding time is 45~600s.This method can realize higher production effect
Rate, but due in composite catalyst contain a certain amount of solvent, such as acetone, Isosorbide-5-Nitrae-dioxane, dimethylbenzene or ethyl acetate, and
Composite catalyst accounting in composition system is larger, and the oder levels and VOC of material are difficult to meet its application field to ring
The requirement of guaranteed cost.
The content of the invention
The invention solves the problems that first technical problem be to provide a kind of environment-friendly and high-performance fast demoulding polyurethane reaction note
Forming composition is penetrated, said composition smell is low, VOC is low, good weatherability, demoulding time are short.
The invention solves the problems that second technical problem be to provide the preparation of self-catalysis chain extender used in said composition a kind of
Method.The self-catalysis chain extender catalytic activity is high, can be used cooperatively with aliphatic isocyanates.
To solve first technical problem, the present invention provides a kind of environment-friendly and high-performance fast demoulding polyurethane reaction and is injected into
Type composition, said composition includes the component of A, B two, as mass fraction including following component：
Component A：PPG 50%~90%, self-catalysis chain extender 1%~10%, chain extender 1%~10%, crosslinking
Agent 1%~20%, pigment 0~8%, age resister 1%~5%, composite catalyst 0.01%~2%, preferably 0.5%~2%；
B component：HMDI 60%~95%, modifying agent 5%~40%, isocyano
(NCO) content 23%~28%.The modifying agent includes at least one dihydric alcohol and at least one trihydroxylic alcohol.The dihydric alcohol bag
Include the one or more in polyoxypropyleneglycol, polytetrahydrofuran diol etc., polyoxypropyleneglycol preferred molecular weight 400~
4000, polytetrahydrofuran diol preferred molecular weight 650~2000.The preferred trimethylolethane of trihydroxylic alcohol, trihydroxy methyl third
One or more in alkane, glycerine etc..
The self-catalysis chain extender refers to the material with following structure：
X=2~5, R is C in formulayH2y+1, y=0~2.
The composite catalyst is formed by isooctyl acid bismuth, isooctyl acid potassium, bicyclic amidine compound and glycerine compounding, multiple
It is with mass ratio：10 parts of isooctyl acid bismuth, isooctyl acid potassium 1~~2 parts, bicyclic 15 parts of amidine compound, 10 parts of glycerine is described double
Ring amidine compound has below general formula：
R in formula1=CaH2a, a=2~4；R2=CbH2b, b=3~7.
The preferred proportion of primary OH groups ＞ 70% of suitable PPG, the oxirane of number-average molecular weight 3000~6500-
One or more in propylene oxide copolyethers triol etc..
The preferred ethylene glycol of suitable chain extender, BDO, 1,3-BDO, diglycol, diethanol amine etc.
In one or more.
The preferred glycerine of suitable crosslinking agent, trimethylolethane, trimethylolpropane, tris(2-hydroxy ethyl)isocyanurate etc.
In one or more.
The preferred 2- of suitable age resister (2 '-hydroxyl -3 ', 5 '-di-tert-butyl-phenyl) -5- chloro benzos triazole, 2-
(2 '-hydroxyl -5 '-aminomethyl phenyl) BTA, double (3,5- three-level butyl -4- hydroxy phenyls) thioethers, double (1,2,2,6,6-
Pentamethyl -4- piperidyls) one or more in sebacate, the monooctyl ester of phosphorous acid three etc..
A kind of method for preparing composition of the present invention, including：
Component A：Each material is added in reactor, is well mixed at 25 DEG C.
B component：Isocyanates and modifying agent are added simultaneously and are heated to 90 DEG C under reaction vessel, stirring, reaction 2~
3h, is cooled to room temperature, discharging.
The self-catalysis type chain extender can be by a kind of progress alkane in piperazine and oxirane, expoxy propane or epoxy butane
Oxygen glycosylation reaction is made, and reaction equation is：
Wherein n, m, h=2~5.
Product is expressed as with formula：
X=2~5, R is C in formulayH2y+1, y=0~2.
To solve second technical problem, the present invention provides a kind of method for preparing self-catalysis chain extender, including following step
Suddenly：Piperazine anhydrous are heated to 65 ± 5 DEG C in the reaction vessel with condensation reflux unit, by epoxy second under temperature constant state
One kind in alkane, expoxy propane or epoxy butane is slowly added dropwise into reaction vessel according to mol ratio, and completion of dropping is warming up to 80
~85 DEG C of reaction 4h, are cooled to after room temperature and discharge.
The present composition has the advantages that compared with prior art：
1. using the self-catalysis chain extender described in invention, dropped in the case of guarantee with aliphatic isocyanates reaction speed
The low consumption of catalyst, while without any organic solvent, without amines catalyst.Compared with prior art
CN103172822A, composite catalyst consumption can reduce by 20%~30%, therefore with lower smell and VOC, the feature of environmental protection is more
It is good.
2. using the self-catalysis chain extender described in invention, the reactivity of system can be effectively improved, and the compound of use is urged
Agent is respectively provided with certain thermal sensitivity with self-catalysis chain extender, and temperature is higher, better to the catalytic effect of polymerization, due to polyurethane
Polymerization process heat release is obvious, thus the reaction of said composition has preferable autoacceleration effect, shortens gel and demoulding time, energy
Enough effectively improve reaction rate.There is higher production efficiency compared to prior art CN103172822A.
3. the special construction having in present composition formula using self-catalysis chain extender, can promote urea in the reaction
The generation of group, and the degree of cross linking is improved, the mechanical property of polymeric material can be improved.Compared to prior art CN103172822A
With higher mechanical property.
4. solvent, amines catalyst are free of in said composition, and because the presence of self-catalysis type chain extender can be substantially reduced
Total usage amount of composite catalyst, CN103172822A compared with prior art, composite catalyst consumption can reduce by 20%~30%,
Therefore with lower smell and VOC, the feature of environmental protection is more preferably.
In summary, the present composition has the advantages that reactivity is high, demoulding time is short, can by reaction injection into
Type (RIM) technique makes high performance polyurethane material, and resulting materials smell is low, VOC is low, good weatherability.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, and number described in following examples is mass parts.
Embodiment 1
(1) synthesis of self-catalysis chain extender：Piperazine anhydrous are heated in the reaction vessel with condensation reflux unit
65 DEG C, in the case where keeping temperature constant state by expoxy propane according to piperazine: expoxy propane=1: 4 mol ratio, it is added dropwise to reaction vessel
In, completion of dropping is warming up to 80~85 DEG C and reacts 4h again, is cooled to after room temperature and discharges.Reaction obtains product structure and is：
(2) preparation of composite catalyst：10 parts of isooctyl acid bismuth, 1 part of isooctyl acid potassium, bicyclic 15 parts of amidine compound, the third three
10 parts of alcohol, it is stand-by after being thoroughly mixed uniformly.
(3) preparation of composition
330N：Epoxy ethane-epoxy propane copolyether triol, 33.5~36.5mgKOH/g of hydroxyl value
Component A：330N, 77.5 parts, 8 parts of the self-catalysis chain extender of above-mentioned preparation, 4 parts of ethylene glycol, trimethylolpropane：8
Part, carbon black：0.5 part, and 2- (2 '-hydroxyl -5 '-aminomethyl phenyl) BTA：0.6 part, double (3,5- three-level butyl -4- hydroxyls
Phenyl) thioether：0.4 part, 1 part of composite catalyst.
B component：HMDI, 90.3 parts, polytetrahydrofuran diol (molecular weight 1000)：
7.5 parts, trimethylolpropane：2.2 part.NCO mass fractions are 26.2%.
(4) technique that example composition A, B prepares PU-RIM materials by high-pressure injection machine is as follows：
1. feed：Component A is added in high-pressure unit A tanks, composition B component is added in B tanks；
2. inject：Set 30~45 DEG C of temperature of charge component A, 30~45 DEG C of B component, 15 ± 3MPa of injection pressure, injection
In the mould that 110~120 DEG C have been heated to mould temperature.
3. it is stripped：As gel time≤10s, the 40s demouldings；As 10~15s of gel time, the 90s demouldings.
4. post curing：1h is cured at 80 DEG C.
Comparative example
Comparative example material manufacture craft is identical with embodiment, and composition components are different, is added without of the present invention from urging
Change chain extender and composite catalyst.
Component A：330N, 76.5 parts, 10 parts of ethylene glycol, trimethylolpropane：10 parts, carbon black：0.5 part, 2- (2 '-hydroxyl-
5 '-aminomethyl phenyl) BTA：0.6 part, double (3,5- three-level butyl -4- hydroxy phenyls) thioethers：0.4 part, contrast patent
2 parts of composite catalyst in CN103172822A.
B component：HMDI, 90.3 parts, polytetrahydrofuran diol (molecular weight 1000)：
7.5 parts, trimethylolpropane：2.2 part.NCO mass fractions are 26.2%.
The embodiment of table 1 is contrasted with comparative example material property
Claims (7)
1. a kind of environment-friendly and high-performance fast demoulding polyurethane reaction injection moulding composition, said composition includes the component of A, B two, press
Mass fraction meter includes following component：
Component A：PPG 50%~90%, self-catalysis chain extender 1%~10%, chain extender 1%~10%, crosslinking agent
1%~20%, pigment 0~8%, age resister 1%~5%, composite catalyst 0.01%~2%；
B component：HMDI 60%~95%, modifying agent 5%~40%, isocyano (NCO)
Content 23%~28%；The modifying agent includes at least one dihydric alcohol and at least one trihydroxylic alcohol；The dihydric alcohol refers to gather
Propylene oxide glycol or polytetrahydrofuran diol and its mixture；The trihydroxylic alcohol is selected from trimethylolethane, trihydroxy methyl third
One or more in alkane, glycerine；
The self-catalysis chain extender refers to the material with following structure：
X=2~5, R is C in formulayH2y+1, y=0~2；
The composite catalyst is formed by isooctyl acid bismuth, isooctyl acid potassium, bicyclic amidine compound and glycerine compounding, compounds matter
Measuring ratio is：10 parts of isooctyl acid bismuth, 1~2 part of isooctyl acid potassium, bicyclic 15 parts of amidine compound, 10 parts of glycerine, the bicyclic amidine class
Compound has below general formula：
R in formula Chinese style1=CaH2a, a=2~4；R2=CbH2b, b=3~7.
2. composition according to claim 1, it is characterized in that polyoxypropyleneglycol molecular weight is 400~4000, poly- four
Hydrogen furans glycol molecular weight is 650~2000.
3. composition according to claim 1, it is characterized in that PPG is selected from proportion of primary OH groups ＞ 70%, number is divided equally
One or more in the epoxy ethane-epoxy propane copolyether triol of son amount 3000~6500.
4. composition according to claim 1, it is characterized in that chain extender is selected from ethylene glycol, BDO, 1,3- fourths two
One or more in alcohol, diglycol, diethanol amine.
5. composition according to claim 1, it is characterized in that crosslinking agent is selected from glycerine, trimethylolethane, three hydroxyl first
One or more in base propane, tris(2-hydroxy ethyl)isocyanurate.
6. composition according to claim 1, it is characterized in that age resister be selected from 2- (2 '-hydroxyl -3 ', 5 '-di-t-butyl
Phenyl) -5- chloro benzos triazole, 2- (2 '-hydroxyl -5 '-aminomethyl phenyl) BTA, double (3,5- three-level butyl -4- hydroxyls
Base phenyl) thioether, double (1,2,2,6,6- pentamethyl -4- piperidyls) sebacates, the one or more in the monooctyl ester of phosphorous acid three.
7. a kind of method of the self-catalysis chain extender prepared described in one of claim 1~6, comprises the following steps：By anhydrous piperazine
Piperazine is heated to 65 ± 5 DEG C in the reaction vessel with condensation reflux unit, under temperature constant state by oxirane, expoxy propane or
One kind in epoxy butane is slowly added dropwise into reaction vessel according to mol ratio, and completion of dropping is warming up to 80~85 DEG C of reaction 4h,
It is cooled to after room temperature and discharges.
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