CN103172822A - Quickly-demoulded weatherproof composition for polyurethane-reaction injection molding and preparation method thereof - Google Patents
Quickly-demoulded weatherproof composition for polyurethane-reaction injection molding and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a quickly-demoulded composition weatherproof composition for polyurethane-reaction injection molding and a preparation method thereof. The composition comprises a component A and a component B, wherein the component A is feed liquid containing an active -OH component, a variety of substances taking the active -OH as a functional group, and a specific catalyst, and if necessary, the component A can also contain an appropriate amount of auxiliary agents including a pigment, an antioxidant, an ultraviolet absorbent, an inner demoulding agent and the like; and the component B is feed liquid containing an active -NCO radical, and consists of 4,4'-dicyclohexyl methane diisocyanate and a modifier. The composition is used for producing a polyurethane product according to an RIM (reaction injection molding) process, wherein the gel time is 8-20 seconds, and the demoulding time is 45-600 seconds; and the storage period of the composition is more than 6 months.
Description
Technical field
The present invention relates to polyurethane field, particularly polyurethane reaction injection molding (PU-RIM) material and technique.
Background technology
Polyurethane reaction injection molding (Polyurethane-Reaction Injection Molding) is called for short PU-RIM, is directly to pass through the Technology of the complicated product of quick response manufacturing from low viscosity, high reaction activity raw material.Various raw materials mutual high velocity impact of moment before entering die cavity mixes, and reacts in die cavity, forms the solid polymer of die cavity shape, completes a molding cycle.The polyurethane reaction injection molding technique is different from casting type polyurethane elastomer, and required little energy is swift in response, and shaping cycle is short.Fully different from traditional thermoplastic injection forming principle, RIM carries out polyreaction in die cavity, rather than by cooling formation solid polymer.The PU-RIM material has good physical and mechanical properties, superior manufacturability and stronger weathering resistance, can satisfy light-weighted requirement simultaneously, thereby be widely used in the numerous areas such as inner and outer decorative parts of the vehicles such as automobile, train, aircraft.
HMDI is commonly called as hydrogenation MDI, is at room temperature colourless to light yellow liquid, and irritant smell is water insoluble, is dissolved in acetone and other organic solvent.Being low to moderate 10～15 ℃ in temperature can crystallization.Therefore, used inconvenience.
ZL200780012104.2 discloses a kind of take HDI and the IPDI PU-RIM material as the basis.IPDI tripolymer and HDI biuret viscosity is large (40 ℃ of lower viscosity of IPDI tripolymer are still in the 5000mpa.s left and right) all, and the IPDI valency is high high than hydrogenation MDI.Material viscosity is a key index that affects two component mixed effects and material property in RIM technique, and to considerable influence is also arranged in work-ing life of RIM machine, more the large equipment load is heavier for viscosity, and high-pressure pump and pipeline are had damage largely, causes the equipment maintenance cost to improve.
Patent documentation US201002225 discloses a kind of technology with the synthetic performed polymer of hydrogenation MDI, adopt the performed polymer of hydrogenation MDI and polyether glycol preparation end NCO group, by sneaking into a certain amount of IPDI monomer, reduce or avoided the crystallization trend of whole prepolymer system.Though this method effectively reduces the Tc of whole system, due to the introducing of monomer I PDI, greatly reduce the reactive behavior of this performed polymer, can cause the decline of material property and production efficiency.
Patent documentation EP0379246A2 discloses a kind of preparation method of the light stable polyurethane that sprays, this patent has comprised a kind of method based on hydrogenation MDI: use the modifier of hydrogenation MDI and the composition of polyvalent alcohol to react by reaction and injection molding process, made in mould can fast demoulding polyurethane material, this material has mechanical property and light stability preferably.Using polyoxyethylene glycol in the method is that modifier carries out modification to hydrogenation MDI, and the reactive behavior of this component be there is no raising.Used general catalyzer and chainextender in patent documentation, and the lead naphthenate that uses is comparatively serious to environmental hazard.
Patent documentation CN101768251A discloses a kind of polyurethane elastomer that is used for automobile glass encapsulation by RIM technique and preparation method thereof.This invention has used aromatic series System Modification isocyanic ester to realize high-performance and fast demoulding, but the light fastness aging of aromatic isocyanate is relatively poor.
Summary of the invention
First technical problem that the present invention solves is to provide a kind of fast demoulding weather resistant polyurethane reaction injection molding composition.
Second technical problem that the present invention solves is to provide a kind of preparation method of said composition.
The present composition comprises A, B two components, the A component is the feed liquid that contains activity-OH component, comprises multiple material take activity-OH as functional group, and comprises specific catalyzer, in case of necessity, also can comprise the auxiliary agents such as appropriate pigment, oxidation inhibitor, uv-absorbing agent, inner pattern releasing agent applicable; The B component is the feed liquid that contains activity-NCO group, is comprised of HMDI and properties-correcting agent.
Fast demoulding weather resistant polyurethane reaction injection molding composition provided by the invention comprises following composition by mass parts:
A component: polyether glycol 50%～90%, chainextender 1%～20%, linking agent 1%～30%, pigment 0～10%, antiaging agent 1%～5%, composite catalyst 0.01%～3%, preferred 0.1%～3%.Described composite catalyst is comprised of organotin, organo-bismuth, organic solvent and dicyclo amidine compound, and organotin is 4～6 parts, and organic solvent is 2～4 parts, and totally 8 parts of organotin and organic solvents, and organo-bismuth is 2 parts, and the dicyclo amidine compound is 15 parts.
Described organotin has following general formula:
In formula: R
3, R
4=C
nH
2n+1N=1～4;
Described organo-bismuth optimization acid bismuth or isocaprylic acid bismuth etc.Described organic solvent can get final product by the catalyst-solvent composition, as acetone, Isosorbide-5-Nitrae-dioxane, dimethylbenzene or ethyl acetate etc.
Described dicyclo amidine compound has following general formula:
In formula: R
1=C
mH
2mM=2～4R
2=C
hH
2hH=3～7;
The preferred proportion of primary OH groups of described polyether glycol＞70%, number-average molecular weight are one or more of 4500～6500 propylene oxide-oxyethane copolyether triol.One or more in the preferred ethylene glycol of described chainextender, BDO, 1,3 butylene glycol, glycol ether, diethanolamine etc.One or more in the preferred trimethylolethane of described linking agent, TriMethylolPropane(TMP) or tris(2-hydroxy ethyl)isocyanurate etc.
B component: hydrogenation MDI60%～95%, properties-correcting agent 5%～40%.Described properties-correcting agent comprises at least a dibasic alcohol and at least a trivalent alcohol.The preferred polyoxypropyleneglycol of dibasic alcohol, polytetrahydrofuran diol or polyester glycol etc., the preferred trimethylolethane of trivalent alcohol, TriMethylolPropane(TMP) or glycerol etc.Described polyoxypropyleneglycol number-average molecular weight is preferred 1000～2000, polytetrahydrofuran diol number-average molecular weight preferred 650～2000.Polyester glycol preferably poly-hexanodioic acid is to comprise that one or more copolymerization in hexanodioic acid and ethylene glycol, butyleneglycol, Diethylene Glycol, triethylene glycol form, number-average molecular weight preferred 2000～3000.Isocyano (NCO) content is 20%～28%.25 ℃ of viscosity 500～1000mPa.s.
A, B constituent mass ratio are 100: 30～130.
The present composition is according to RIM explained hereafter polyurethane product, gel time 8～20s, and demould time 45～600s, composition storage period is more than 6 months.
If need color, can add appropriate pigment such as carbon black etc. in the A component, can adjust in 0～10% scope according to the color depth amount of pigment.
Reaction and injection molding process polyurethane composition of the present invention can be prepared by following methods:
A component: polyether glycol, chainextender, linking agent, composite catalyst, pigment, antiaging agent are added in reactor, mix under 25 ℃.
The B component: isocyanic ester and properties-correcting agent are added reaction vessel simultaneously, be heated to 90 ℃ under stirring, reaction 2～3h is cooled to the room temperature discharging.
Composition of the present invention adopts RIM technique to be injected in 45～600s demoulding in mould, takes out goods, places 1 all slakings at 80 ℃ of temperature under slaking 0.5～1h or normal temperature, and the gained polyurethane material has following performance:
Density: 1.00～1.03g/cm
3
Hardness: Shao Shi 50～95A
Tensile strength: 5～15MPa
Tear strength: 10～40N/mm.
Organo-metallic composite catalyst used in the present invention is specially adapted to hydrogenation MDI system, and the reaction of this system is had extremely strong katalysis, can greatly improve the reactive behavior of A component; Can significantly improve the speed of reaction of system, make the polymerization degree increase rapidly, can significantly shorten gel and demould time.And not leaded, mercury, cadmium have greatly reduced the harm to environment.
The present invention uses dibasic alcohol and trivalent alcohol jointly hydrogenation MDI to be carried out modification, has improved the average functionality of B component, makes this component show higher speed of reaction in reaction, has significantly shortened the demould time of goods in RIM technique.And make system obtain higher polymerization crosslinking degree, material property further improves.
Composition of the present invention is the aliphatics system, does not contain benzene ring structure, compares with the aromatic series system that contains MDI, TDI, has superior light aging resisting advantage; Compare with belonging to aliphatic IPDI, composition of the present invention adopts ammonia ester modified, and viscosity is less, and is having larger advantage aspect material fluidity, mold filling character, also less to the wearing and tearing of RIM equipment.
The material appearance glossiness of using composition and method of making the same of the present invention to produce is high, good mechanical performance, light aging resisting property are excellent, be applicable to make the exterior trimming parts of the vehicles such as automobile, train, aircraft, be specially adapted to the products such as vehicles glass edge-wrapping integral window.
Embodiment
Below the invention will be further described by concrete embodiment.Umber described in following examples is mass parts.
The preparation of embodiment composite catalyst: the dibutyl tin laurate of 1 part, 5 part of two lauric acid tin methide and 2 parts of acetone are added in container, at room temperature mix, then add the Bismuth Octoate of 2 parts and mix, add again 15 parts of 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chloro benzo triazole, obtain composite catalyst.
The B component: be heated to 90 ℃ under isocyanic ester and properties-correcting agent, stirring, reaction 3h is cooled to the room temperature discharging.
The technique that example composition A, B component are passed through the standby PU-RIM material of RIM mechanism is as follows:
1. reinforced: as according to formula, composition A component premix to be joined in the A component storage tank of high-pressure injection machine after evenly, then take a certain amount of composition B component and join in B component storage tank;
2. injection: set 30～45 ℃ of temperature of charge A components, 30～45 ℃ of B components, injection pressure 15 ± 3MPa is expelled in the mould that is preheated to 110～120 ℃;
3. the demoulding: when gel time≤10s, the 45s demoulding; When gel time 10～15s, the 120s demoulding;
4. post curing: slaking 1h at 80 ℃ of temperature.
330N: epoxy ethane-epoxy propane copolyether triol, hydroxyl value 33.5-36.5mgKOH/g.
Embodiment 1
The A component: 330N:73 part, ethylene glycol: 10 parts, TriMethylolPropane(TMP): 10 parts, carbon black: 0.5 part, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole: 0.6 part; Two (three grades of butyl of 3,5--4-hydroxy phenyl) thioether: 0.4 part; Composite catalyst: 1.5 parts.
The B component: hydrogenation MDI:80.1 part, TriMethylolPropane(TMP): 1.8 parts, poly adipate succinic acid ester (molecular weight 3000): 18.1 parts.The NCO massfraction is 23.5%.25 ℃ of viscosity 800mPa.s.
Comparative Examples 1
The A component: 330N:73 part, ethylene glycol: 10 parts, Diethylene Glycol: 10 parts, carbon black: 0.5 part, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole: 1.6 parts; Two (three grades of butyl of 3,5--4-hydroxy phenyl) thioether: 1.4 parts; Dibutyl tin laurate: 1 part, 1,8-diazabicylo-dicyclo (5,4,0)-7-hendecene: 1 part.
B component: with embodiment 1.
Comparative Examples 1 '
The A component: 330N:73 part, ethylene glycol: 10 parts, TriMethylolPropane(TMP): 10 parts, carbon black: 0.5 part, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole: 1.6 parts; Two (three grades of butyl of 3,5--4-hydroxy phenyl) thioether: 1.4 parts; Dibutyl tin laurate: 1 part, triethylene diamine: 1 part.
B component: with embodiment 1.
Embodiment 2
The A component: 330N:71.2 part, ethylene glycol: 18 parts, TriMethylolPropane(TMP): 3 parts, carbon black: 2 parts, 2-(2 '-hydroxyl-3,5 '-di-tert-butyl-phenyl)-5-chloro benzo triazole: 2 parts; Two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate: 1 part; Composite catalyst: 2.8 parts.
The B component: hydrogenation MDI:90.1 part, TriMethylolPropane(TMP): 2.4 parts, polytetrahydrofuran diol (molecular weight 1000): 7.5 parts.The NCO massfraction is 26.0%.25 ℃ of viscosity 500mPa.s.
Comparative Examples 2
A component: with embodiment 2.
B component: hydrogenation MDI:85 part, poly adipate succinic acid ester (molecular weight 3000): 15 parts.The NCO massfraction is 26.8%.
Embodiment 3
The A component: 330N:67.5 part, ethylene glycol: 15 parts, TriMethylolPropane(TMP): 10 parts, carbon black: 2.5 parts, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole: 1.6 parts; Two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate: 1.4 parts; Composite catalyst: 2 parts.
The B component: hydrogenation MDI:89.1 part, TriMethylolPropane(TMP): 6.4 parts, poly-adipate glycol-butanediol ester (molecular weight 2000): 4.5 parts.The NCO massfraction is 22.6%.25 ℃ of viscosity 800mPa.s.
Comparative Examples 3
A component: 330N:100 part, BDO: 10 parts, 2-amido-2-ethyl-1,3-PD: 5 parts, lead naphthenate: 0.5 part, 1,8-diazabicylo-dicyclo (5,4,0)-7-hendecene: 1.5 parts, phosphonous acid triphenyl ester: 0.8 part, 2-(2-hydroxyl-3,5-two tertiary amyls-phenyl)-2H-benzotriazole: 0.4 part, pigment: 5 parts.
B component: hydrogenation MDI:81.3 part, polyoxyethylene glycol (molecular weight 400): 18.7 parts.The NCO massfraction is 22.1%.
Embodiment 4
The A component: 330N:79.5 part, ethylene glycol: 10 parts, TriMethylolPropane(TMP): 3 parts, carbon black: 2.5 parts, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole: 1.6 parts; Two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate: 1.4 parts; Composite catalyst: 2 parts.
The B component: hydrogenation MDI:89.1 part, TriMethylolPropane(TMP): 6.4 parts, poly-adipate glycol-butanediol ester (molecular weight 2000): 4.5 parts.The NCO massfraction is 22.6%.25 ℃ of viscosity 800mPa.s.
The speed of response contrast of the composition of each embodiment of table 1
Each embodiment of table 2 prepares the mechanical property of PU-RIM material
Claims (10)
1. fast demoulding weather resistant polyurethane reaction injection molding composition comprises following composition by mass parts:
A component: polyether glycol 50%～90%, chainextender 1%～20%, linking agent 1%～30%, pigment 0～10%, antiaging agent 1%～5%, composite catalyst 0.01%～3%; Described composite catalyst is comprised of organotin, organo-bismuth, organic solvent and dicyclo amidine compound, and organotin is 4～6 parts, and organic solvent is 2～4 parts, and totally 8 parts of organotin and organic solvents, and organo-bismuth is 2 parts, and the dicyclo amidine compound is 15 parts;
Described organotin has following general formula:
In formula: R
3, R
4=C
nH
2n+1N=1～4;
Described dicyclo amidine compound has following general formula:
In formula: R
1=C
mH
2mM=2～4R
2=C
hH
2hH=3～7;
The B component: hydrogenation MDI60%～95%, properties-correcting agent 5%～40%, described properties-correcting agent comprise at least a dibasic alcohol and at least a trivalent alcohol;
A, B constituent mass ratio are 100: 30～130.
2. composition according to claim 1, is characterized in that described organo-bismuth refers to bismuth carboxylate or isocaprylic acid bismuth.
3. composition according to claim 2, is characterized in that polyether glycol described in the A component is proportion of primary OH groups＞70%, and number-average molecular weight is one or more of 4500～6500 propylene oxide-oxyethane copolyether triol; Described chainextender refers to one or more in ethylene glycol, BDO, 1,3 butylene glycol, glycol ether or diethanolamine; Described linking agent refers to one or more in trimethylolethane, TriMethylolPropane(TMP) or tris(2-hydroxy ethyl)isocyanurate; Described organic solvent refers to acetone, Isosorbide-5-Nitrae-dioxane, dimethylbenzene or ethyl acetate.
4. composition according to claim 3, is characterized in that described in the B component, dibasic alcohol refers to polyoxypropyleneglycol, polytetrahydrofuran diol or polyester glycol; Trivalent alcohol refers to select trimethylolethane, TriMethylolPropane(TMP) or glycerol.
5. composition according to claim 4, is characterized in that in the B component, the polyoxypropyleneglycol number-average molecular weight is 1000～2000, and the polytetrahydrofuran diol number-average molecular weight is 650～2000.
6. composition according to claim 4 is characterized in that polyester glycol in the B component refers to that one or more copolymerization in hexanodioic acid and ethylene glycol, butyleneglycol, Diethylene Glycol, triethylene glycol form, and number-average molecular weight is 2000～3000.
7. composition according to claim 4, is characterized in that B component isocyano (NCO) content is 20%～28%; 25 ℃ of viscosity are 500～1000mPa.s.
8. one of according to claim 1～7 described compositions, is characterized in that composition according to RIM explained hereafter polyurethane product, and gel time is 8～20s, and demould time is 45～600s, and composition storage period is more than 6 months.
9. one of according to claim 1～7 described compositions, is characterized in that adopting RIM technique to be injected in 45～600s demoulding in mould, takes out goods, places 1 all slakings at 80 ℃ of temperature under slaking 0.5～1h or normal temperature, and the gained polyurethane material has following performance:
Density: 1.00～1.03g/cm
3
Hardness: Shao Shi 50～95A
Tensile strength: 5～15MPa
Tear strength: 10～40N/mm.
10. method for preparing the described composition of one of claim 1～9 comprises the following steps:
A component: polyether glycol, chainextender, linking agent, composite catalyst, pigment, antiaging agent are added in reactor, mix under 25 ℃;
The B component: isocyanic ester and properties-correcting agent are added reaction vessel simultaneously, be heated to 90 ℃ under stirring, reaction 2～3h is cooled to the room temperature discharging.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107189028A (en) * | 2017-06-23 | 2017-09-22 | 黎明化工研究设计院有限责任公司 | A kind of preparation method of environment-friendly and high-performance fast demoulding polyurethane reaction injection moulding composition and its self-catalysis chain extender |
| CN111718462A (en) * | 2020-04-15 | 2020-09-29 | 黎明化工研究设计院有限责任公司 | Self-skinning polyurethane foam rapid demoulding composition for automobile steering wheel and preparation method thereof |
| CN115746618A (en) * | 2022-11-23 | 2023-03-07 | 黎明化工研究设计院有限责任公司 | Internal release agent, self-releasing double-component self-repairing transparent polyurethane coating and preparation method thereof |
| CN116178669A (en) * | 2023-03-08 | 2023-05-30 | 安徽开捷汽车部件有限公司 | High-toughness reaction injection molding material and application thereof |
| CN117285842A (en) * | 2023-11-24 | 2023-12-26 | 黎明化工研究设计院有限责任公司 | Modified color paste, bi-component aromatic polyurethane material and preparation method thereof |
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Cited By (10)
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| CN107189028A (en) * | 2017-06-23 | 2017-09-22 | 黎明化工研究设计院有限责任公司 | A kind of preparation method of environment-friendly and high-performance fast demoulding polyurethane reaction injection moulding composition and its self-catalysis chain extender |
| CN107189028B (en) * | 2017-06-23 | 2020-02-28 | 黎明化工研究设计院有限责任公司 | Environment-friendly high-performance rapid demoulding polyurethane reaction injection molding composition and preparation method of autocatalysis chain extender thereof |
| CN111718462A (en) * | 2020-04-15 | 2020-09-29 | 黎明化工研究设计院有限责任公司 | Self-skinning polyurethane foam rapid demoulding composition for automobile steering wheel and preparation method thereof |
| CN111718462B (en) * | 2020-04-15 | 2021-12-31 | 黎明化工研究设计院有限责任公司 | Self-skinning polyurethane foam rapid demoulding composition for automobile steering wheel and preparation method thereof |
| CN115746618A (en) * | 2022-11-23 | 2023-03-07 | 黎明化工研究设计院有限责任公司 | Internal release agent, self-releasing double-component self-repairing transparent polyurethane coating and preparation method thereof |
| CN115746618B (en) * | 2022-11-23 | 2024-04-05 | 黎明化工研究设计院有限责任公司 | Internal release agent, self-release bi-component self-repairing transparent polyurethane coating and preparation method thereof |
| CN116178669A (en) * | 2023-03-08 | 2023-05-30 | 安徽开捷汽车部件有限公司 | High-toughness reaction injection molding material and application thereof |
| CN116178669B (en) * | 2023-03-08 | 2024-05-14 | 安徽开捷汽车部件有限公司 | High-toughness reaction injection molding material and application thereof |
| CN117285842A (en) * | 2023-11-24 | 2023-12-26 | 黎明化工研究设计院有限责任公司 | Modified color paste, bi-component aromatic polyurethane material and preparation method thereof |
| CN117285842B (en) * | 2023-11-24 | 2024-02-27 | 黎明化工研究设计院有限责任公司 | Modified color paste, bi-component aromatic polyurethane material and preparation method thereof |
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