CN104961876A - Thermoplastic hard polyurethane foam plastic for automobile interior decoration and preparation method thereof - Google Patents
Thermoplastic hard polyurethane foam plastic for automobile interior decoration and preparation method thereof Download PDFInfo
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- CN104961876A CN104961876A CN201510324695.3A CN201510324695A CN104961876A CN 104961876 A CN104961876 A CN 104961876A CN 201510324695 A CN201510324695 A CN 201510324695A CN 104961876 A CN104961876 A CN 104961876A
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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
- 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
- C08G18/65—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
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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
- 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
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- 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
- 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
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
Abstract
The invention belongs to the technical field of chemical engineering materials, and particularly relates to thermoplastic hard polyurethane foam plastic for automobile interior decoration and a preparation method thereof. The thermoplastic hard polyurethane foam plastic is composed of a component A and a component B, the component A is composed of rapeseed oil derivative, polyether polyol, polyester polyol, crosslinking agent, H2O, foam stabilizer, hole opening agent, foaming catalyst and gel catalyst, and the component B is modified MDI. By the preparation method, foam which is lower in density, high in hole opening ratio and elongation rate, good in elongation effect and high in mechanical performance can be prepared, and requirements, on automobile ceiling interior decoration, of premium cars are met.
Description
Technical field
The invention belongs to chemical material technical field, be specifically related to a kind of automotive trim foamed thermoplastic hard polyurethane plastic and preparation method thereof.
Background technology
In recent years, the China Automobile Industry of China is swift and violent, and car presents the growth of explosive type.Along with the fast development of automobile, the lightweight, comfortableness etc. of automobile have more and more become the focus of people's concern.Automotive interior material, as the important component part of automobile, has caused the attention that people are enough.Foamed thermoplastic hard polyurethane plastic has incomparable superiority, progressively replaces other materials, is widely used in the manufacture of automotive interior roof, and the ceiling made by it has the high-performances such as light weight, heat insulation, sound-absorbing.
Polyhydric alcohol conjugate material, as the raw material prepared thermoplastic polyurethane and hard bubble, comprises multiple polyvalent alcohol and auxiliary agent, whipping agent etc.On the one hand, current conventional polyether polyols derives from oil, along with oil price costliness can affect environment protection in recent years simultaneously, therefore exploitation natural materials is badly in need of with petroleum replacing goods, the polyurethane foam overwhelming majority simultaneously generally applied uses freonll-11, the whipping agents such as 141b, all there is destruction to atmospheric layer, full water foamed system is owing to only generating carbonic acid gas in foaming process, become the foaming system most with environmental protection characteristic, global density is ensured as whipping agent owing to needing a large amount of water, and water and isocyanate reaction generate large calorimetric, the problem such as easily cause foam heartburn.On the other hand, in medium-to-high grade vehicle, along with light-weighted development trend, also to being decorated with higher mechanical property requirements in ceiling, these all result in canopy system higher technical threshold.
Therefore Application and Development has higher economic worth in the environment-friendly type low density heat plasticity rigid urethane foam of automotive trim.
Summary of the invention
The object of this invention is to provide a kind of automotive trim foamed thermoplastic hard polyurethane plastic, environmental protection, cost be low, high opening rate, higher unit elongation, preferably extension effect and preferably mechanical property; Invention also provides the preparation method of automotive trim foamed thermoplastic hard polyurethane plastic, scientific and reasonable, simple.
Automotive trim foamed thermoplastic hard polyurethane plastic of the present invention, is made up of component A and B component, and the weight ratio of component A and B component is 1: 1.7-1.8, wherein,
Component A is made up of the raw material of following weight percent:
B component is modification MDI.
Described rapeseed oil derivative is the alcoholysis product of rapeseed oil and small molecule polyol, and wherein small molecule polyol is one or more in ethylene glycol, propylene glycol, glycerine, TriMethylolPropane(TMP), trolamine or tetramethylolmethane.
Described trolamine is the good fossilisation Products in Fushun, and glycerine is Shanghai grease factory product, and TriMethylolPropane(TMP) is Sheng Tianhengchuan bio tech ltd, Hubei product.
Described rapeseed oil is Hubei life grease limited-liability company commercially available prod.
The preparation method of described rapeseed oil derivative, step is as follows:
(1) take rapeseed oil and small molecule polyol is poured in reactor, adding PbO is catalyzer, after logical nitrogen replacement, starts to stir, and is warming up to 150-250 DEG C of reaction 1.5-2.5 hour simultaneously, obtains rapeseed oil derivative;
(2) add oxidation inhibitor in a kettle., 75-85 DEG C is stirred 0.5-1.5h, stirs fully and releases.
The mol ratio of the small molecule polyol described in step (1) and rapeseed oil is 1.8-2.0: 1.
PbO consumption described in step (1) is the 0.7-0.9% of small molecule polyol weight, preferably 0.8%.
Oxidation inhibitor described in step (2) is that its consumption is the 0.5-0.8% of small molecule polyol weight without BHT liquid phenols complex type antioxidant; Be preferably the mixture of ChicPU3318 and ChicF96 (Shanghai Qi Kefu silicon materials company limited, commercially available prod), both weight ratios are 1:3-3:1.
Described polyether glycol is polyether glycol A and polyether glycol B; Polyether glycol A is YNW-210E (Shandong Inov New Material Co., Ltd.), hydroxyl value is 127 ± 5, viscosity is 150 ± 30, take propylene glycol as initiator, KOH is catalyzer, after propylene oxide ring-opening polymerization, with ethylene oxide-capped polyether polyol with high activity, oxyethane accounts for 27% of pfpe molecule amount; Polyether glycol B is YNW-304T (Shandong Inov New Material Co., Ltd. commercially available prod), and hydroxyl value is 380 ± 5.
Described polyester polyol is 6255 (Fu Sheng commercially available prod, Jiangsu).
Described linking agent is GJ9701 (Gaoqiao Petrochemical Company commercially available prod); Suds-stabilizing agent is B8870 (winning wound companies market product); Pore-creating agent is O-501, viscosity 150-400, relative density 0.9-1, Nanjing ancient cooking vessel chemistry technology & development Co. in morning commercially available prod; Kicker is the mixture of A-33 and DMDEE, and the weight ratio of A-33 and DMDEE is 1-2:2.7-3.5; Gel catalyst is organic tin catalyzer, the sub-tin T-9 of preferably octanoic acid.
Described modification MDI is DG5412, and this is Shandong Inov Polyurethane Co., Ltd. commercially available prod.
The preparation method of automotive trim foamed thermoplastic hard polyurethane plastic of the present invention, step is as follows:
(1) preparation of component A: then add water, kicker, gel catalyst, suds-stabilizing agent, linking agent, pore-creating agent by stirring 10-15min in the rapeseed oil derivative of preparation, polyether glycol, polyester polyol loading reactor, stirring reaction at normal temperatures, stir 2-3 hour, get final product barrelling for subsequent use;
(2) preparation of B component: modification MDI is weighed for subsequent use;
During use, component A and B component are passed through high pressure casting molding machine Homogeneous phase mixing, injects mould, through overmolding slaking, obtained product.
The key of dealing with problems is: one is find suitable natural materials petroleum replacing product synthesizing polyether, solve petroleum product substitution problem, in polyethers, select suitable oxidation inhibitor to solve the heartburn problem existed when environment-friendly type full water premixed systems downstream application simultaneously; Two is under the collocation by polyether glycol system, polyester system, suitable suds-stabilizing agent, catalyzer etc., prepares the foam at lower densities with higher unit elongation and preferably extension effect.
The present invention compared with prior art, has following beneficial effect:
The present invention is main polyether components with rapeseed oil derivative, solve petroleum product substitution problem, in preparation process, add oxidation inhibitor simultaneously, solve the heartburn problem existed when environment-friendly type full water premixed systems downstream application, environmental protection, cost is low, simultaneously premixed systems is with under rapeseed oil and alcoholysate thereof the prerequisite that is main component, by selecting polyether glycol system, polyester polyol, suitable suds-stabilizing agent, catalyzer, pore-creating agent etc., prepare and can have high opening rate under lower density, higher unit elongation and preferably extension effect, the preferably foam of mechanical property, meet high-grade car for the requirement of roof of the vehicle interior trim.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
(1) preparation of rapeseed oil derivative:
Get small molecule polyol mixture (trolamine, glycerine and TriMethylolPropane(TMP) mol ratio are 3:5:2) 20Kg, the mol ratio of they and rapeseed oil is 2: 1, pour in reactor, add the PbO catalyzer of 0.16Kg, after logical nitrogen replacement, start to stir, be warming up to 210 DEG C of reactions 2.5 hours simultaneously, obtain rapeseed oil derivative (i.e. alcoholysis product); Add PU3318 oxidation inhibitor 0.075Kg and ChicF96 oxidation inhibitor 0.025Kg afterwards in a kettle., 85 DEG C are stirred 1h, stir fully and release.
(2) preparation of component A:
10min is stirred by the rapeseed oil derivative of above-mentioned preparation, polyether glycol, polyester polyol loading reactor, then water, kicker, gel catalyst, suds-stabilizing agent, linking agent, pore-creating agent is added, stirring reaction at normal temperatures, stirs 3 hours, gets final product barrelling for subsequent use;
(3) preparation of B component: DG5412 is weighed for subsequent use.
(4) be 1: 1.7 by high pressure casting molding machine Homogeneous phase mixing by above-mentioned component A and B component DG5412 according to weight ratio, inject mould, through overmolding slaking, obtained product, product performance index is as shown in table 1 after testing.
Embodiment 2
(1) preparation of rapeseed oil derivative:
Take small molecule polyol mixture (trolamine, glycerine and TriMethylolPropane(TMP) mol ratio are 2:3:5) 20Kg, the mol ratio of they and rapeseed oil is 1.9: 1, pour in reactor, add the PbO catalyzer of 0.16Kg, after logical nitrogen replacement, start to stir, be warming up to 250 DEG C of reactions 1.5 hours simultaneously, obtain rapeseed oil derivative (i.e. alcoholysis product); Add PU3318 oxidation inhibitor 0.025Kg and ChicF96 oxidation inhibitor 0.075Kg afterwards in a kettle., 80 DEG C are stirred 1.5h, stir fully and release.
(2) preparation of component A:
15min is stirred by the rapeseed oil derivative of above-mentioned preparation, polyether glycol, polyester polyol loading reactor, then water, kicker, gel catalyst, suds-stabilizing agent, linking agent, pore-creating agent is added, stirring reaction at normal temperatures, stirs 2 hours, gets final product barrelling for subsequent use;
(3) preparation of B component: DG5412 is weighed for subsequent use.
(4) be 1: 1.75 by high pressure casting molding machine Homogeneous phase mixing by above-mentioned component A and B component DG5412 according to weight ratio, inject mould, through overmolding slaking, obtained product, product performance index is as shown in table 1 after testing.
Embodiment 3
(1) preparation of rapeseed oil derivative:
Take small molecule polyol mixture (trolamine, glycerine and TriMethylolPropane(TMP) mol ratio are 2:5:3) 20Kg, the mol ratio of they and rapeseed oil is 2: 1, pour in reactor, add the PbO catalyzer of 0.16Kg, after logical nitrogen replacement, start to stir, be warming up to 230 DEG C of reactions 2 hours simultaneously, obtain rapeseed oil derivative (i.e. alcoholysis product); Two is add PU3318 oxidation inhibitor 0.05KG and ChicF96 oxidation inhibitor 0.05Kg in a kettle., and about 75 DEG C are stirred 0.5h, stirs fully and releases.
(2) preparation of component A:
12min is stirred by the rapeseed oil derivative of above-mentioned preparation, polyether glycol, polyester polyol loading reactor, then water, kicker, gel catalyst, suds-stabilizing agent, linking agent, pore-creating agent is added, stirring reaction at normal temperatures, stirs 2.5 hours, gets final product barrelling for subsequent use;
(3) preparation of B component: DG5412 is weighed for subsequent use.
(4) be 1: 1.8 by high pressure casting molding machine Homogeneous phase mixing by above-mentioned component A and B component DG5412 according to weight ratio, inject mould, through overmolding slaking, obtained product, product performance index is as shown in table 1 after testing.
The product fundamental property index that table 1 embodiment 1-3 is obtained
As seen from the above table: the environment-friendly type low density heat plasticity rigid urethane foam being applied to automotive trim obtained by embodiment, all more than 90%, there is not heartburn problem in foamed open cell rate; Foam core density is at 21-23kg/m simultaneously
3, mechanical property meets national standard completely, and this foam is described, and mechanical property is more excellent at lower densities.
Claims (10)
1. an automotive trim foamed thermoplastic hard polyurethane plastic, is made up of component A and B component, it is characterized in that the weight ratio of component A and B component is 1: 1.7-1.8, wherein,
Component A is made up of the raw material of following weight percent:
B component is modification MDI.
2. automotive trim foamed thermoplastic hard polyurethane plastic according to claim 1, it is characterized in that described rapeseed oil derivative is the alcoholysis product of rapeseed oil and small molecule polyol, wherein small molecule polyol is one or more in ethylene glycol, propylene glycol, glycerine, TriMethylolPropane(TMP), trolamine or tetramethylolmethane.
3. automotive trim foamed thermoplastic hard polyurethane plastic according to claim 2, it is characterized in that the preparation method of described rapeseed oil derivative, step is as follows:
(1) take rapeseed oil and small molecule polyol is poured in reactor, adding PbO is catalyzer, after logical nitrogen replacement, starts to stir, and is warming up to 150-250 DEG C of reaction 1.5-2.5 hour simultaneously, obtains rapeseed oil derivative;
(2) add oxidation inhibitor in a kettle., 75-85 DEG C is stirred 0.5-1.5h, stirs fully and releases.
4. automotive trim foamed thermoplastic hard polyurethane plastic according to claim 3, is characterized in that the mol ratio of the small molecule polyol described in step (1) and rapeseed oil is 1.8-2.0: 1.
5. automotive trim foamed thermoplastic hard polyurethane plastic according to claim 3, is characterized in that the PbO consumption described in step (1) is the 0.7-0.9% of small molecule polyol weight.
6. automotive trim foamed thermoplastic hard polyurethane plastic according to claim 3, it is characterized in that the oxidation inhibitor described in step (2) is that its consumption is the 0.5-0.8% of small molecule polyol weight without BHT liquid phenols complex type antioxidant.
7. automotive trim foamed thermoplastic hard polyurethane plastic according to claim 1, is characterized in that described polyether glycol is polyether glycol A and polyether glycol B; Polyether glycol A is YNW-210E, and hydroxyl value is 127 ± 5, and viscosity is 150 ± 30, take propylene glycol as initiator, KOH is catalyzer, after propylene oxide ring-opening polymerization, with ethylene oxide-capped polyether polyol with high activity, oxyethane accounts for 27% of pfpe molecule amount; Polyether glycol B is YNW-304T, and hydroxyl value is 380 ± 5.
8. automotive trim foamed thermoplastic hard polyurethane plastic according to claim 1, is characterized in that described polyester polyol is 6255.
9. automotive trim foamed thermoplastic hard polyurethane plastic according to claim 1, is characterized in that described linking agent is GJ9701; Suds-stabilizing agent is B8870; Pore-creating agent is O-501; Kicker is the mixture of A-33 and DMDEE, and the weight ratio of A-33 and DMDEE is 1-2:2.7-3.5; Gel catalyst is organic tin catalyzer.
10. a preparation method for the arbitrary described automotive trim foamed thermoplastic hard polyurethane plastic of claim 1-9, is characterized in that step is as follows:
(1) preparation of component A: then add water, kicker, gel catalyst, suds-stabilizing agent, linking agent, pore-creating agent by stirring 10-15min in the rapeseed oil derivative of preparation, polyether glycol, polyester polyol loading reactor, stirring reaction at normal temperatures, stir 2-3 hour, get final product barrelling for subsequent use;
(2) preparation of B component: modification MDI is weighed for subsequent use;
During use, component A and B component are passed through high pressure casting molding machine Homogeneous phase mixing, injects mould, through overmolding slaking, obtained product.
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| CN201510324695.3A CN104961876B (en) | 2015-06-11 | 2015-06-11 | Automotive trim foamed thermoplastic hard polyurethane plastic and preparation method thereof |
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| CN201510324695.3A CN104961876B (en) | 2015-06-11 | 2015-06-11 | Automotive trim foamed thermoplastic hard polyurethane plastic and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105315423A (en) * | 2015-11-17 | 2016-02-10 | 山东一诺威新材料有限公司 | Continuous production-type all-water low-density acoustical board material and preparation method thereof |
| CN105524248A (en) * | 2015-12-18 | 2016-04-27 | 山东蓝星东大化工有限责任公司 | Polyether combination material for vehicle door inner side wall and preparation method thereof |
| CN106243315A (en) * | 2016-08-30 | 2016-12-21 | 烟台正海合泰科技股份有限公司 | A kind of roof of the vehicle the PU cystosepiment of low plasticization temperature and production technology thereof |
| CN106543700A (en) * | 2016-10-31 | 2017-03-29 | 江苏昊晟塑业科技有限公司 | For the expanded material of roof of the vehicle |
| CN106632952A (en) * | 2016-12-27 | 2017-05-10 | 万华化学（北京）有限公司 | Thermoformable polyurethane foam and preparation method thereof |
| CN108610621A (en) * | 2018-05-16 | 2018-10-02 | 宁波拓普集团股份有限公司 | A kind of high acoustic absorption low-density polyurethane semi-rigid foam and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105315423A (en) * | 2015-11-17 | 2016-02-10 | 山东一诺威新材料有限公司 | Continuous production-type all-water low-density acoustical board material and preparation method thereof |
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| CN105524248A (en) * | 2015-12-18 | 2016-04-27 | 山东蓝星东大化工有限责任公司 | Polyether combination material for vehicle door inner side wall and preparation method thereof |
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| CN106543700A (en) * | 2016-10-31 | 2017-03-29 | 江苏昊晟塑业科技有限公司 | For the expanded material of roof of the vehicle |
| CN106632952A (en) * | 2016-12-27 | 2017-05-10 | 万华化学（北京）有限公司 | Thermoformable polyurethane foam and preparation method thereof |
| CN106632952B (en) * | 2016-12-27 | 2019-12-13 | 万华化学（北京）有限公司 | polyurethane foam capable of being thermoformed and preparation method thereof |
| CN108610621A (en) * | 2018-05-16 | 2018-10-02 | 宁波拓普集团股份有限公司 | A kind of high acoustic absorption low-density polyurethane semi-rigid foam and preparation method thereof |
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| CN104961876B (en) | 2017-12-05 |
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Address after: Linzi District of Shandong Province Jin Shan Zhen Feng Guan Lu 255400 Zibo City No. 58 Applicant after: SHANDONG INOV NEW MATERIAL CO., LTD. Address before: 255400 Shandong Province, Zibo city Linzi District South East Nanshan Road West five by ethylene Applicant before: SHANDONG INOV NEW MATERIAL CO., LTD. |
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| GR01 | Patent grant | ||
| GR01 | Patent grant |