CN103172822B - 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 PDF

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CN103172822B
CN103172822B CN201310129646.5A CN201310129646A CN103172822B CN 103172822 B CN103172822 B CN 103172822B CN 201310129646 A CN201310129646 A CN 201310129646A CN 103172822 B CN103172822 B CN 103172822B
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composition
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glycol
polyurethane
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CN103172822A (en
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孙嘉鹏
董火成
朱小树
李宁
于文杰
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Liming Research Institute of Chemical Industry Co Ltd
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Liming Research Institute of Chemical Industry Co Ltd
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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

A kind of fast demoulding weather resistant polyurethane reaction injection molding composition and preparation method thereof
Technical field
The present invention relates to polyurethane field, particularly polyurethane reaction injection molding (PU-RIM) materials and process.
Background technology
Polyurethane reaction injection molding (Polyurethane-Reaction Injection Molding) is called for short PU-RIM, be directly from low viscosity, high reaction activity raw material by the Technology of the complicated product of quick response manufacturing.Various raw material is moment high velocity impact mixing mutually before entering die cavity, and reacts in die cavity, forms the solid polymer of mold cavity shapes, completes a molding cycle.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.Completely different from traditional thermoplastic injection forming principle, RIM carries out polyreaction in die cavity, instead of forms solid polymer by cooling.PU-RIM material has good physical and mechanical properties, superior manufacturability and stronger weathering resistance, can meet light-weighted requirement simultaneously, thus be widely used in the numerous areas such as the 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 DEG C in temperature can crystallization.Therefore, inconvenience has been used.
ZL200780012104.2 discloses a kind of PU-RIM material based on HDI and IPDI.IPDI tripolymer and HDI biuret viscosity all comparatively large (at IPDI tripolymer 40 DEG C, viscosity is still at about 5000mpa.s), and IPDI valency height comparatively hydrogenation MDI is high.Material viscosity is the key index affecting two component mixed effects and material property in RIM technique, and also have considerable influence to the work-ing life of RIM machine, more large equipment load is heavier for viscosity, has damage largely high-pressure pump and pipeline, causes equipment maintenance cost to improve.
Patent documentation US201002225 discloses a kind of technology of synthesizing performed polymer with hydrogenation MDI, hydrogenation MDI and polyether glycol is adopted to prepare the performed polymer holding NCO group, by being mixed into a certain amount of IPDI monomer, reduce or avoid 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, the decline of material property and production efficiency can be caused.
Patent documentation EP0379246A2 discloses a kind of preparation method of the light stable polyurethane sprayed, this patent contains a kind of method based on hydrogenation MDI: use the modifier of hydrogenation MDI and the composition of polyvalent alcohol to be reacted by reaction and injection molding process, obtaining in a mold can the polyurethane material of fast demoulding, and this material has good mechanical property and light stability.Use polyoxyethylene glycol system modifier to carry out modification to hydrogenation MDI in the method, raising be there is no to the reactive behavior of this component.Employ general catalyzer and chainextender in patent documentation, and the lead naphthenate used is comparatively serious to environmental hazard.
Patent documentation CN101768251A discloses a kind of by the polyurethane elastomer and preparation method thereof of RIM technique for automobile glass encapsulation.This invention employs aromatic system modified isocyanate and achieves high-performance and fast demoulding, but the light fastness aging of aromatic isocyanate is 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 component, component A is the feed liquid containing activity-OH component, comprises the multiple material being functional group with activity-OH, and comprises specific catalyzer, if desired, also the auxiliary agents such as appropriate pigment, oxidation inhibitor, uv-absorbing agent, inner pattern releasing agent applicable can be comprised; B component is the feed liquid containing activity-NCO group, is made up 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:
Component A: polyether glycol 50% ~ 90%, chainextender 1% ~ 20%, linking agent 1% ~ 30%, pigment 0 ~ 10%, antiaging agent 1% ~ 5%, composite catalyst 0.01% ~ 3%, preferably 0.1% ~ 3%.Described composite catalyst is made up of organotin, organo-bismuth, organic solvent and dicyclo amidine compound, and organotin is 4 ~ 6 parts, and organic solvent is 2 ~ 4 parts, and organotin and organic solvent totally 8 parts, organo-bismuth is 2 parts, and 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 energy 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 > 70% of described polyether glycol, number-average molecular weight is one or more of the propyleneoxide-ethyleneoxide copolyether triol of 4500 ~ 6500.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 one dibasic alcohol and at least one 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 preferably 1000 ~ 2000, polytetrahydrofuran diol number-average molecular weight preferably 650 ~ 2000.Polyester glycol is poly-hexanodioic acid system preferably, and one or more copolymerization comprised in hexanodioic acid and ethylene glycol, butyleneglycol, Diethylene Glycol, triethylene glycol form, number-average molecular weight preferably 2000 ~ 3000.Isocyano (NCO) content is 20% ~ 28%.25 DEG C of viscosity 500 ~ 1000mPa.s.
A, B component mass ratio are 100: 30 ~ 130.
The present composition is according to RIM explained hereafter polyurethane product, and gel time 8 ~ 20s, demould time 45 ~ 600s, composition storage period is more than 6 months.
If need color, appropriate pigment can be added as carbon black etc. in component A, can adjust in the scope of 0 ~ 10% according to color depth amount of pigment.
Reaction and injection molding process polyurethane composition of the present invention, can be prepared by following methods:
Component A: polyether glycol, chainextender, linking agent, composite catalyst, pigment, antiaging agent are added in reactor, mixes at 25 DEG C.
B component: isocyanic ester and properties-correcting agent are added reaction vessel simultaneously, is heated to 90 DEG C under stirring, reaction 2 ~ 3h, is cooled to room temperature discharging.
Composition of the present invention adopts RIM technique to be injected in 45 ~ 600s demoulding in mould, takes out goods, and place slaking in 1 week under slaking 0.5 ~ 1h or normal temperature at 80 DEG C of temperature, gained polyurethane material has following performance:
Density: 1.00 ~ 1.03g/cm 3
Hardness: shore 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, has extremely strong katalysis to the reaction of this system, greatly can improve the reactive behavior of component A; The speed of reaction of system can be significantly improved, make the polymerization degree increase rapidly, can significantly shorten gel and demould time.And not leaded, mercury, cadmium, greatly reduce the harm to environment.
The present invention uses dibasic alcohol and trivalent alcohol jointly to carry out modification to hydrogenation MDI, improves the average functionality of B component, makes this component show higher speed of reaction in the reaction, significantly shorten the demould time of goods in RIM technique.And make system obtain higher polymerization crosslinking degree, material property improves further.
Composition of the present invention is aliphatic systems, not containing benzene ring structure, compared with the aromatic system containing MDI, TDI, has superior light aging resisting advantage; With belong to compared with aliphatic IPDI, composition of the present invention adopts ammonia ester modified, and viscosity is less, in material fluidity, mold filling character, have larger advantage, also less to the wearing and tearing of RIM equipment.
The material appearance glossiness using composition and method of making the same of the present invention to produce is high, good mechanical performance, light aging resisting property excellent, be applicable to the exterior trimming parts manufacturing the vehicles such as automobile, train, aircraft, be specially adapted to the products such as vehicles glass edge-wrapping integral window.
Embodiment
Below by way of concrete embodiment, the invention will be further described.Number described in following examples is mass parts.
The preparation of embodiment composite catalyst: the dibutyl tin laurate of 1 part, 5 parts of dilaurate and 2 parts of acetone are added in container, at room temperature be uniformly mixed, then add the Bismuth Octoate of 2 parts and be uniformly mixed, add again 15 parts of 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chloro benzo triazole, obtain composite catalyst.
B component: isocyanic ester and properties-correcting agent, is heated to 90 DEG C under stirring, reaction 3h, is cooled to room temperature discharging.
Example composition A, B component are as follows by the technique of the standby PU-RIM material of RIM mechanism:
1. feed in raw material: according to formula, by composition component A premix evenly after join in the component A storage tank of high-pressure injection machine, then take a certain amount of composition B component and join in B component storage tank;
2. inject: setting temperature of charge component A 30 ~ 45 DEG C, B component 30 ~ 45 DEG C, injection pressure 15 ± 3MPa, is expelled in the mould being preheated to 110 ~ 120 DEG C;
3. the demoulding: as gel time≤10s, the 45s demoulding; As gel time 10 ~ 15s, the 120s demoulding;
4. post curing: slaking 1h at 80 DEG C of temperature.
330N: epoxy ethane-epoxy propane copolyether triol, hydroxyl value 33.5-36.5mgKOH/g.
Embodiment 1
Component A: 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 (3,5-, tri-grades of butyl-4-hydroxy phenyls) thioether: 0.4 part; Composite catalyst: 1.5 parts.
B component: hydrogenation MDI:80.1 part, TriMethylolPropane(TMP): 1.8 parts, poly adipate succinic acid ester (molecular weight 3000): 18.1 parts.NCO massfraction is 23.5%.25 DEG C of viscosity 800mPa.s.
Comparative example 1
Component A: 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 (3,5-, tri-grades of butyl-4-hydroxy phenyls) 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 example 1 '
Component A: 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 (3,5-, tri-grades of butyl-4-hydroxy phenyls) thioether: 1.4 parts; Dibutyl tin laurate: 1 part, triethylene diamine: 1 part.
B component: with embodiment 1.
Embodiment 2
Component A: 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.
B component: hydrogenation MDI:90.1 part, TriMethylolPropane(TMP): 2.4 parts, polytetrahydrofuran diol (molecular weight 1000): 7.5 parts.NCO massfraction is 26.0%.25 DEG C of viscosity 500mPa.s.
Comparative example 2
Component A: with embodiment 2.
B component: hydrogenation MDI:85 part, poly adipate succinic acid ester (molecular weight 3000): 15 parts.NCO massfraction is 26.8%.
Embodiment 3
Component A: 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.
B component: hydrogenation MDI:89.1 part, TriMethylolPropane(TMP): 6.4 parts, poly-adipate glycol-butanediol ester (molecular weight 2000): 4.5 parts.NCO massfraction is 22.6%.25 DEG C of viscosity 800mPa.s.
Comparative example 3
Component A: 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-bis-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.NCO massfraction is 22.1%.
Embodiment 4
Component A: 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.
B component: hydrogenation MDI:89.1 part, TriMethylolPropane(TMP): 6.4 parts, poly-adipate glycol-butanediol ester (molecular weight 2000): 4.5 parts.NCO massfraction is 22.6%.25 DEG C of viscosity 800mPa.s.
The speed of response contrast of the composition of each embodiment of table 1
The each embodiment of table 2 prepares the mechanical property of PU-RIM material

Claims (10)

1. a fast demoulding weather resistant polyurethane reaction injection molding composition, comprises following composition by mass parts:
Component A: 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 made up of organotin, organo-bismuth, organic solvent and dicyclo amidine compound, and organotin is 4 ~ 6 parts, and organic solvent is 2 ~ 4 parts, and organotin and organic solvent totally 8 parts, organo-bismuth is 2 parts, and 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;
Described polyether glycol is proportion of primary OH groups > 70%, and number-average molecular weight is one or more of the propyleneoxide-ethyleneoxide copolyether triol of 4500 ~ 6500; Described linking agent refer in trimethylolethane, TriMethylolPropane(TMP) or tris(2-hydroxy ethyl)isocyanurate one or more;
B component: hydrogenation MDI 60% ~ 95%, properties-correcting agent 5% ~ 40%, described properties-correcting agent comprises at least one dibasic alcohol and at least one trivalent alcohol;
A, B component mass ratio are 100: 30 ~ 130.
2. composition according to claim 1, is characterized in that described organo-bismuth refers to isocaprylic acid bismuth.
3. composition according to claim 2, it is characterized in that chainextender described in component A refers in ethylene glycol, BDO, 1,3 butylene glycol, glycol ether or diethanolamine one or more; Described organic solvent refers to acetone, Isosorbide-5-Nitrae-dioxane, dimethylbenzene or ethyl acetate.
4. composition according to claim 3, is characterized in that dibasic alcohol described in B component refers to polyoxypropyleneglycol, polytetrahydrofuran diol or polyester glycol; Trivalent alcohol refers to and selects trimethylolethane, TriMethylolPropane(TMP) or glycerol.
5. composition according to claim 4, it is characterized in that in B component, polyoxypropyleneglycol number-average molecular weight is 1000 ~ 2000, polytetrahydrofuran diol number-average molecular weight is 650 ~ 2000.
6. composition according to claim 4, it is characterized in that polyester glycol in B component refers to that one or more copolymerization in hexanodioic acid and ethylene glycol, butyleneglycol, Diethylene Glycol, triethylene glycol form, 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 DEG C of viscosity are 500 ~ 1000mPa.s.
8. according to the composition one of claim 1 ~ 7 Suo Shu, it is characterized in that composition is according to RIM explained hereafter polyurethane product, gel time is 8 ~ 20s, and demould time is 45 ~ 600s, and composition storage period is more than 6 months.
9., according to the composition one of claim 1 ~ 7 Suo Shu, it is characterized in that adopting RIM technique to be injected in 45 ~ 600s demoulding in mould, take out goods, place slaking in 1 week under slaking 0.5 ~ 1h or normal temperature at 80 DEG C of temperature, gained polyurethane material has following performance:
Density: 1.00 ~ 1.03g/cm 3
Hardness: shore 50 ~ 95A
Tensile strength: 5 ~ 15MPa
Tear strength: 10 ~ 40N/mm.
10. prepare a method for the described composition of one of claim 1 ~ 9, comprise the following steps:
Component A: polyether glycol, chainextender, linking agent, composite catalyst, pigment, antiaging agent are added in reactor, mixes at 25 DEG C;
B component: isocyanic ester and properties-correcting agent are added reaction vessel simultaneously, is heated to 90 DEG C under stirring, reaction 2 ~ 3h, is cooled to room temperature discharging.
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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
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
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
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
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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US4362824A (en) * 1981-05-29 1982-12-07 Texaco Inc. Method for making RIM polyurethane elastomers using as the catalyst system dimethylethanolamine, dibutyltin dilaurate and an alkyltin mercaptide
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CN102336882B (en) * 2011-06-17 2013-04-10 黎明化工研究院 Environmentally-friendly storage-stable polyurethane composition for reaction injection molding and preparation method thereof

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