CN104961876B - Automotive trim foamed thermoplastic hard polyurethane plastic and preparation method thereof - Google Patents
Automotive trim foamed thermoplastic hard polyurethane plastic and preparation method thereof Download PDFInfo
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- CN104961876B CN104961876B CN201510324695.3A CN201510324695A CN104961876B CN 104961876 B CN104961876 B CN 104961876B CN 201510324695 A CN201510324695 A CN 201510324695A CN 104961876 B CN104961876 B CN 104961876B
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- hard polyurethane
- rapeseed oil
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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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to chemical material technical field, and in particular to a kind of automotive trim foamed thermoplastic hard polyurethane plastic and preparation method thereof.Automotive trim is made up of with foamed thermoplastic hard polyurethane plastic component A and B component, component A：Rapeseed oil derivative, PPG, PEPA, crosslinking agent, H2O, foam stabiliser, pore-creating agent, kicker, gel catalyst, B component：Modified MDI.The present invention prepares can have high opening rate, higher elongation percentage and preferably extension effect, the foam of preferably mechanical property under lower density, meet high-grade car for roof of the vehicle interior trim requirement.
Description
Technical field
The invention belongs to chemical material technical field, and in particular to a kind of automotive trim thermoplastic hard polyurethane foam
Plastics and preparation method thereof.
Background technology
In recent years, the China Automobile Industry in China is swift and violent, and the growth of explosion type is presented in car.With the quick hair of automobile
Exhibition, the lightweight of automobile, comfortableness etc. has increasingly becomed focus of concern.Weight of the automotive interior material as automobile
Part is wanted, has triggered the attention that people are enough.Foamed thermoplastic hard polyurethane plastic has incomparable excellent
More property, progressively substitutes other materials, is widely used in the manufacture of automotive interior roof, has matter by the ceiling of its making
The superior functions such as gently, heat-insulated, sound-absorbing.
Polyhydric alcohol conjugate material is as the raw material for preparing thermoplastic polyurethane hard bubble, including a variety of polyalcohols and auxiliary agent, foaming
Agent etc..On the one hand, conventional polyether polyols derive from oil at present, can influence environment simultaneously as oil price is expensive in recent years
Protection, therefore it is badly in need of exploitation natural material to substitute petroleum product, while the most uses of commonly used polyurethane foam
The foaming agents such as freon, 141b, there is destruction to atmosphere, full water foamed system in foaming process due to only generating dioxy
Change carbon, turn into the foaming system of most environmental protection characteristic, due to needing substantial amounts of water as foaming agent guarantee global density, and water
Big calorimetric is generated with isocyanates reaction, easily causes the problems such as foam is heartburn.On the other hand, it is adjoint in medium-to-high grade vehicle
Light-weighted development trend, also to being decorated with higher mechanical property requirements in ceiling, these, which have resulted in canopy system, has
Higher technical threshold.
Therefore development and application have higher in the environment-friendly type low density heat plasticity RPUF of automotive trim
Economic value.
The content of the invention
It is an object of the invention to provide a kind of automotive trim foamed thermoplastic hard polyurethane plastic, environmental protection, cost be low,
High opening rate, preferably higher elongation percentage, extension effect and preferably mechanical property；Invention also provides automotive trim
It is scientific and reasonable, simple and easy with the preparation method of foamed thermoplastic hard polyurethane plastic.
Automotive trim foamed thermoplastic hard polyurethane plastic of the present invention, is made up of component A and B component, A groups
Divide and the weight ratio of B component is 1: 1.7-1.8, wherein,
Component A is made up of the raw material of following percentage by weight：
B component is modified 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, propane diols, glycerine, trimethylolpropane, triethanolamine or pentaerythrite.
Described triethanolamine is the good fossilisation Products in Fushun, and glycerine is Shanghai grease factory product, trihydroxy methyl third
Alkane is Hubei Sheng Tianhengchuan bio tech ltd product.
Described rapeseed oil is Hubei life grease limited company commercially available prod.
The preparation method of described rapeseed oil derivative, step are as follows：
(1) rapeseed oil is weighed to pour into reactor with small molecule polyol, addition PbO is catalyst, after leading to nitrogen displacement,
Start to stir, while be warming up to 150-250 DEG C of reaction 1.5-2.5 hour, obtain rapeseed oil derivative；
(2) antioxidant is added in a kettle, 75-85 DEG C of stirring 0.5-1.5h, is released after stirring fully.
The mol ratio of small molecule polyol and rapeseed oil described in step (1) is 1.8-2.0: 1.
PbO dosages described in step (1) are the 0.7-0.9% of small molecule polyol weight, preferably 0.8%.
Antioxidant described in step (2) is that its dosage is small molecule polyol without BHT liquid phenols complex type antioxidants
The 0.5-0.8% of weight；Preferably ChicPU3318 and ChicF96 (Shanghai Qi Kefu silicon materials Co., Ltd, commercially available prod)
Mixture, both weight ratios be 1:3-3:1.
Described PPG is PPG A and PPG B；PPG A is YNW-210E (Shandong
One Nowe new material Co., Ltd), hydroxyl value is 127 ± 5, and viscosity is 150 ± 30, and using propane diols as initiator, KOH is catalysis
After agent, with expoxy propane ring-opening polymerisation, with ethylene oxide-capped polyether polyol with high activity, oxirane accounts for pfpe molecule amount
27%；PPG B is YNW-304T (Shandong Inov New Material Co., Ltd. commercially available prod), and hydroxyl value is 380 ± 5.
Described PEPA is 6255 (Jiangsu Fu Sheng commercially available prod).
Described crosslinking agent is GJ9701 (Gaoqiao Petrochemical Company commercially available prod)；Foam stabiliser is that B8870 (wins wound companies market
Product)；Pore-creating agent is O-501, viscosity 150-400, relative density 0.9-1, the commercially available production of Nanjing ancient cooking vessel morning chemistry technology ＆ development Co.
Product；Kicker is A-33 and DMDEE mixture, and A-33 and DMDEE weight ratio are 1-2:2.7-3.5；Gel is catalyzed
Agent is organic tin catalyst, preferably octanoic acid stannous T-9.
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 are as follows：
(1) preparation of component A：Rapeseed oil derivative, PPG, the PEPA of preparation are fitted into reactor
Then stirring 10-15min adds water, kicker, gel catalyst, foam stabiliser, crosslinking agent, pore-creating agent, in normal temperature
Lower stirring reaction, stir 2-3 hours, you can barrelling is standby；
(2) preparation of B component：It is standby that MDI weighings will be modified；
In use, component A is uniformly mixed with B component by high pressure casting machine, mould is injected, is cured through overmolding, made
Obtain product.
The key solved the problems, such as is：First, finding suitable natural material substitutes oil product synthesizing polyether, solves stone
Oil product substitution problem, while solve to deposit in the full water combination material downstream application of environment-friendly type from suitable antioxidant in polyethers
Heartburn problem；Second, the collocation by PPG system, polyester system, suitable foam stabiliser, catalyst etc.
Under, preparing at lower densities has higher elongation percentage and the preferably foam of extension effect.
The present invention compared with prior art, has the advantages that：
The present invention solves petroleum product substitution problem, while preparing using rapeseed oil derivative as main polyether components
Antioxidant is added in journey, solves the existing heartburn problem in the full water combination material downstream application of environment-friendly type, environmental protection, cost are low, together
Shi Zuhe material using rapeseed oil and its alcoholysate as main component on the premise of, by selecting PPG system, polyester polyols
Alcohol, suitable foam stabiliser, catalyst, pore-creating agent etc., high opening rate, higher can be had under lower density by preparing
The foam of elongation percentage and preferably extension effect, preferably mechanical property, meeting high-grade car will for roof of the vehicle interior trim
Ask.
Embodiment
The present invention is described further with reference to embodiments.
Embodiment 1
(1) preparation of rapeseed oil derivative：
Taking small molecule polyol mixture, (triethanolamine, glycerine and trimethylolpropane mol ratio are 3:5:2) 20Kg, it
With the mol ratio of rapeseed oil be 2: 1, pour into reactor, add 0.16Kg PbO catalyst, after leading to nitrogen displacement, start
Stirring, while be warming up to 210 DEG C and react 2.5 hours, obtain rapeseed oil derivative (i.e. alcoholysis product)；Add in a kettle afterwards
Enter PU3318 antioxidant 0.075Kg and ChicF96 antioxidant 0.025Kg, 85 DEG C of stirring 1h, released after stirring fully.
(2) preparation of component A：
Rapeseed oil derivative, PPG, the PEPA of above-mentioned preparation are fitted into reactor and stir 10min,
Then water, kicker, gel catalyst, foam stabiliser, crosslinking agent, pore-creating agent are added, stirring reaction, is stirred at normal temperatures
Mix 3 hours, you can barrelling is standby；
(3) preparation of B component：DG5412 is weighed standby.
(4) above-mentioned component A is uniformly mixed according to weight ratio with B component DG5412 for 1: 1.7 by high pressure casting machine, noted
Enter mould, cured through overmolding, product is made, product performance index is as shown in table 1 after testing.
Embodiment 2
(1) preparation of rapeseed oil derivative：
Weighing small molecule polyol mixture, (triethanolamine, glycerine and trimethylolpropane mol ratio are 2:3:5) 20Kg,
Their mol ratios with rapeseed oil are 1.9: 1, pour into reactor, add 0.16Kg PbO catalyst, after leading to nitrogen displacement,
Start to stir, while be warming up to 250 DEG C and react 1.5 hours, obtain rapeseed oil derivative (i.e. alcoholysis product)；Afterwards in reactor
Middle addition PU3318 antioxidant 0.025Kg and ChicF96 antioxidant 0.075Kg, 80 DEG C of stirring 1.5h, is released after stirring fully.
(2) preparation of component A：
Rapeseed oil derivative, PPG, the PEPA of above-mentioned preparation are fitted into reactor and stir 15min,
Then water, kicker, gel catalyst, foam stabiliser, crosslinking agent, pore-creating agent are added, stirring reaction, is stirred at normal temperatures
Mix 2 hours, you can barrelling is standby；
(3) preparation of B component：DG5412 is weighed standby.
(4) above-mentioned component A is uniformly mixed according to weight ratio with B component DG5412 for 1: 1.75 by high pressure casting machine,
Mould is injected, is cured through overmolding, product is made, product performance index is as shown in table 1 after testing.
Embodiment 3
(1) preparation of rapeseed oil derivative：
Weighing small molecule polyol mixture, (triethanolamine, glycerine and trimethylolpropane mol ratio are 2:5:3) 20Kg,
Their mol ratios with rapeseed oil are 2: 1, pour into reactor, add 0.16Kg PbO catalyst, after leading to nitrogen displacement, open
Begin to stir, while be warming up to 230 DEG C and react 2 hours, obtain rapeseed oil derivative (i.e. alcoholysis product)；Second, add in a kettle
Enter PU3318 antioxidant 0.05KG and ChicF96 antioxidant 0.05Kg, 75 DEG C or so stirring 0.5h, released after stirring fully.
(2) preparation of component A：
Rapeseed oil derivative, PPG, the PEPA of above-mentioned preparation are fitted into reactor and stir 12min,
Then water, kicker, gel catalyst, foam stabiliser, crosslinking agent, pore-creating agent are added, stirring reaction, is stirred at normal temperatures
Mix 2.5 hours, you can barrelling is standby；
(3) preparation of B component：DG5412 is weighed standby.
(4) above-mentioned component A is uniformly mixed according to weight ratio with B component DG5412 for 1: 1.8 by high pressure casting machine, noted
Enter mould, cured through overmolding, product is made, product performance index is as shown in table 1 after testing.
Product basic performance indices made from the embodiment 1-3 of table 1
As seen from the above table：As the environment-friendly type low density heat plasticity hard polyurethane applied to automotive trim obtained by embodiment
Ester foamed plastic, foamed open cell rate is more than 90%, in the absence of heartburn problem；Foam core density is in 21-23kg/m simultaneously3,
Mechanical property complies fully with national standard, and illustrating this foam, mechanical property is more excellent at lower densities.
Claims (8)
1. a kind of automotive trim foamed thermoplastic hard polyurethane plastic, is made up of, it is characterised in that A A components and B components
The weight of component and B components ratio is 1: 1.7-1.8, wherein,
A components are made up of the raw material of following percentage by weight：
Rapeseed oil derivative 30-40%
PPG 20-35%
PEPA 20-40%
Crosslinking agent 0.5-1.5%
H2O 5-7%
Foam stabiliser 0.8-1.2%
Pore-creating agent 0.2-0.5%
Kicker 0.2-0.5%
Gel catalyst 0.2-0.5%；
B components are modified MDI；
Described PPG is PPG A and PPG B；PPG A is YNW-210E, and hydroxyl value is
127 ± 5, viscosity is 150 ± 30, and using propane diols as initiator, KOH is catalyst, after expoxy propane ring-opening polymerisation, uses epoxy
The polyether polyol with high activity of ethane end-blocking, oxirane account for the 27% of pfpe molecule amount；PPG B is YNW-304T, hydroxyl
It is worth for 380 ± 5；
Described crosslinking agent is GJ9701；Foam stabiliser is B8870；Pore-creating agent is O-501；Kicker be A-33 with
DMDEE mixture, A-33 and DMDEE weight ratio are 1-2:2.7-3.5；Gel catalyst is organic tin catalyst.
2. automotive trim foamed thermoplastic hard polyurethane plastic according to claim 1, it is characterised in that described
Rapeseed oil derivative is the alcoholysis product of rapeseed oil and small molecule polyol, wherein small molecule polyol be ethylene glycol, propane diols,
One or more in glycerine, trimethylolpropane, triethanolamine or pentaerythrite.
3. automotive trim foamed thermoplastic hard polyurethane plastic according to claim 2, it is characterised in that described
The preparation method of rapeseed oil derivative, step are as follows：
（1）Weigh rapeseed oil to pour into reactor with small molecule polyol, addition PbO is catalyst, after leading to nitrogen displacement, is started
Stirring, while 150-250 DEG C of reaction 1.5-2.5 hour is warming up to, obtain rapeseed oil derivative；
（2）Antioxidant is added in a kettle, 75-85 DEG C of stirring 0.5-1.5h, is released after stirring fully.
4. automotive trim foamed thermoplastic hard polyurethane plastic according to claim 3, it is characterised in that step（1）
Described in small molecule polyol and rapeseed oil mol ratio be 1.8-2.0: 1.
5. automotive trim foamed thermoplastic hard polyurethane plastic according to claim 3, it is characterised in that step（1）
Described in PbO dosages be small molecule polyol weight 0.7-0.9%.
6. automotive trim foamed thermoplastic hard polyurethane plastic according to claim 3, it is characterised in that step（2）
Described in antioxidant be without BHT liquid phenols complex type antioxidants, its dosage is the 0.5- of small molecule polyol weight
0.8%.
7. automotive trim foamed thermoplastic hard polyurethane plastic according to claim 1, it is characterised in that described
PEPA is 6255.
8. a kind of preparation method of any described automotive trim foamed thermoplastic hard polyurethane plastics of claim 1-7,
It is characterized in that step is as follows：
（1）The preparation of component A：Rapeseed oil derivative, PPG, the PEPA of preparation are fitted into reactor and stirred
Then 10-15min adds water, kicker, gel catalyst, foam stabiliser, crosslinking agent, pore-creating agent, stir at normal temperatures
Reaction is mixed, stirs 2-3 hours, you can barrelling is standby；
（2）The preparation of B components：It is standby that MDI weighings will be modified；
In use, component A is uniformly mixed with B component by high pressure casting machine, mould is injected, is cured through overmolding, production is made
Product.
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| CN105315423B (en) * | 2015-11-17 | 2018-01-30 | 山东一诺威新材料有限公司 | A kind of full water low density acoustic plate material of continous way type of production and preparation method thereof |
| CN105524248B (en) * | 2015-12-18 | 2018-12-04 | 山东蓝星东大化工有限责任公司 | Car door inner sidewall polyether combined material 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 |
| 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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| CN1844184A (en) * | 2006-04-27 | 2006-10-11 | 南京红宝丽股份有限公司 | Rigid polyurethane foam prepared by using rape seed oil |
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