CN103254395A - Nanometer calcium carbonate-filled polyurethane high-resilience molding foam and preparation method thereof - Google Patents
Nanometer calcium carbonate-filled polyurethane high-resilience molding foam and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nanometer calcium carbonate-filled polyurethane high-resilience molding foam which is characterized by comprising the following raw materials in parts by weight: 50 to 70 parts of polyether polyol, 15 to 25 parts of polymer polyol, 15 to 25 parts of nanometer calcium carbonate, 0.2 to 0.3 part of dimethyl amino ethyl ether, 0.7 to 1.0 part of gel catalyst, 0.8 to 1.2 parts of a foam homogenizing agent, 0.5 to 0.8 part of polyurethane surfactant, 1.5 to 2 parts of a cross-linking agent, 1 to 2 parts of an opening agent and 3 to 4 parts of water. The invention further discloses a preparation method for the high-pressure foaming of the nanometer calcium carbonate-filled polyurethane high-resilience molding foam. The molding foam disclosed by the invention is low in cost, good in mechanical property, good in load-carrying property and low in VOC (volatile organic compounds) discharge. By lightly changing a high-pressure foaming machine, the high-pressure foaming of the nanometer calcium carbonate can be realized, so that the product homogeneity is improved effectively.
Description
Technical field
The present invention relates to a kind of polyurethane foam and preparation method thereof, particularly polyurethane high-elastic moulded foam of a kind of nano-calcium carbonate filling and preparation method thereof.
Background technology
What use in the automobile seat is polyurethane high-elastic molded foam plastics product, according to the difference of vehicle, load-carrying properties and the comfortableness of foam article is had different requirements.For the general technical scheme of the present manufacturer of the load-carrying properties that improve goods is to add a kind of organic petrochemical material (following general designation POP) that is called polymer polyatomic alcohol in prescription.The consumption of pop reaches polyether glycol: polymer polyatomic alcohol is 50:50, and its relative merits are as follows:
Advantage: in composition of raw materials, add a certain proportion of POP, can promote the load-carrying properties of high rebound foam goods; Can improve simultaneously the process tolerance of production process.
Shortcoming: getting attribute owing to POP is petrochemical complex, and product cost is quite high, and average in recent years market value is 15-16 unit/kilogram.
Next is that to produce POP be to be that masterbatch+vinylbenzene+propylene is fine with polyether glycol, carries out the polymerization chain link by the customizations construction equipment and reacts and get.The fine two kinds of raw materials of vinylbenzene wherein and propylene all belong to the poisonous and harmful chemical element, and therefore, the foam article of producing does not reach the environmental requirement that country limits the quantity of to air organism volatilization in the passenger car.Therefore seek the alternative or partly alternative POP of a kind of energy and can improve the foam article load-carrying properties again, the starting material that reduce VOC become the main direction of present insider's research.
Chinese patent application 201010173350.x discloses foam material that a kind of nanometer grade calcium carbonate filled polypropylene/polyethylene blend makes and preparation method thereof, the inside is filled into nano-calcium carbonate in the foam materials, improves resistance to impact shock and the physical and mechanical properties of product.Reduce cost.Add nano inorganic material and become reduction VOC, a megatrend that reduces cost, but present high pressure foaming machine comprises foaming machine storage tank (1), in the outlet of foaming machine storage tank (1) strainer (2) is set, and in the outlet of described strainer (2) high-pressure metering pump is set.No matter be import equipment or home equipment, the plunger type high-pressure volume pump that the German BOSCH-REXROTH that the overwhelming majority all is to use is produced, minority is used Beijing Glan BOSCH-REXROTH plunger type high-pressure volume pump.Inorganic nano material easily causes damage to ram pump, on the one hand because this plunger accuracy requirement is very high, in case damage parts in wearing and tearing or the pump occurs, just can only scrap, can't keep in repair, the cost height, the price of this pump itself is also very expensive in addition, and one about 3-6 is ten thousand yuan.Secondly, this pump is not with self-suction function, and depended on pressure container type storage tank is given the feed end transferring raw material of pump, in case during the storage tank insufficient pressure, will directly have influence on the rated flow of pump, causes the fluctuation of quality product consistence.Therefore, nano-calcium carbonate is using high pressure foaming machine to carry out the also use of polyurethane high-elastic molded foam plastics production field.
Summary of the invention
For solving above technical problem, the object of the present invention is to provide a kind of low cost of manufacture, VOC is low, has solved the high resilience moulded foam of nano-calcium carbonate filled polyurethane of foam article load-carrying properties again.Another object of the present invention is to provide the preparation method of the high-pressure foam of this kind foam materials.
The present invention seeks to realize like this: the high resilience moulded foam of a kind of nano-calcium carbonate filled polyurethane, it is characterized in that: the following starting material by parts by weight are made: polyether glycol 50-70 part, polymer polyatomic alcohol 15-25 part, nano-calcium carbonate 15-25 part, dimethyl aminoethyl ether 0.2-0.3 part, gel catalyst 0.7-1.0 part, foam stabilizer 0.8-1.2 part, polyurethane surfactant 0.5-0.8 part, linking agent 1.5-2 part, pore-creating agent 1-2 part, water 3-4 part.
Adopt technique scheme, with nano-calcium carbonate instead of part polymer polyatomic alcohol (POP), thereby reduce the consumption of POP greatly, reduced cost, also reduced the influence of VOC simultaneously, and added the foam of the foam materials of inorganic nano calcium carbonate, excellent in cushion effect, the mechanical property excellence, load-carrying properties are good, and comfortableness is good.Product detects through the national SGS TVOC of inspection center and reaches national limit standard.
In technique scheme: described gel catalyst is triethylene diamine.
Another object of the present invention is achieved in that a kind of method for preparing the high resilience moulded foam of nano-calcium carbonate filled polyurethane, finishes according to following steps:
(1), according to the proportioning in the claim 1, polyether glycol, polymer polyatomic alcohol and nano-calcium carbonate are put into the high speed reactor, high-speed stirring makes fully mixes;
(2), the material that mixes of step (1) changes in the low speed isothermal reaction still, adds dimethyl aminoethyl ether, gel catalyst, foam stabilizer, polyurethane surfactant, linking agent, pore-creating agent and water, keeps 22-28 ℃ of temperature, stirs standby;
(3), gained material in the step (2) is transferred to carries out high-pressure foam in the high pressure foaming machine, described high pressure foaming machine comprises foaming machine storage tank (1), in the outlet of foaming machine storage tank (1) strainer (2) is set, pump (3) is set in the outlet of described strainer (2), described pump (3) is the duplex straight-tooth conjugate crescent seal gear pump, described duplex straight-tooth conjugate crescent seal gear pump is connected with high-pressure mixing head (4) by pipeline, and the pipeline between duplex straight-tooth conjugate crescent seal gear pump and high-pressure mixing head (4) is provided with under meter (5); Material in the described step (2) is transferred to earlier in the storage tank (1) of high pressure foaming machine, passing through strainer (2) then filters, material is delivered to high-pressure mixing head (4) through pump (3) again, and material is cast to foaming in the foam mold (7) by high-pressure mixing head (4).
Adopt aforesaid method, the ram pump in the high pressure foaming machine is replaced with the duplex straight-tooth conjugate crescent seal gear pump, do not change other configurations of whole equipment.The low price of this pump of one side, one only needs 1600-2000 unit, and this pump can reach pressure and the traffic requirement of high pressure foaming machine, efficient energy-saving.Secondly because this pump is toothed gear pump, meshing between the interocclusal clearance accuracy requirement not high, when adding inorganic nano material, even pump is produced wearing and tearing, still do not influence pressure and the flow of high pressure foaming machine.Secondly, this pump self has self-suction function, and feeder system pressure is required to improve greatly, and homogeneity of product is effectively promoted.The present invention does high pressure foaming machine after the above-mentioned change, makes the polyurethane foam of having added inorganic nano calcium carbonate can realize high-pressure foam, and material cost can directly reduce 8%-10%.
In technique scheme: described pump (3) adopts variable-frequency motor control.
Control for convenience in technique scheme: described high pressure foaming machine also comprises control unit (6), described under meter (5) passes to control unit (6) with flow signal, described control unit (6) passes the signal along to the frequency transformer (8) of the variable-frequency motor of pump (3), and described frequency transformer (8) is adjusted pump (3) output frequency.
In technique scheme: in the step (1), stirring velocity is 130-150 commentaries on classics/min, churning time 30-45min.
In technique scheme: in the described step (2), stirring velocity is 35-45 commentaries on classics/min.
In technique scheme: the temperature of described foam mold is 50-60 ℃, dwell time 300-360s
Beneficial effect: polyurethane high-elastic moulded foam cost of the present invention is low, good mechanical property, and load-carrying properties are good, and the VOC discharging is low.And the present invention only does slight change to high pressure foaming machine, just can realize the high-pressure foam of nano-calcium carbonate, and homogeneity of product is effectively promoted.
Description of drawings
Fig. 1 is the structural representation of urethane high-pressure foam of the present invention;
Fig. 2 is schematic circuit of the present invention.
Embodiment
Shown in Fig. 1-2, urethane high pressure foaming machine of the present invention is mainly by foaming machine storage tank 1, strainer 2, pump 3, high-pressure mixing head 4, under meter 5, control unit 6 parts such as grade are formed, the structure of described urethane high pressure foaming machine is prior art, do not do at this and to give unnecessary details, key is, outlet at foaming machine storage tank 1 arranges strainer 2, pump 3 is set in the outlet of described strainer 2, described pump 3 is the duplex straight-tooth conjugate crescent seal gear pump, (this pump configuration can be with reference to ZL201220431753.4 to comprise the back pump of the front pump of a low pressure and mass flow and a high-pressure low-flow and a pump shaft, do not do at this and to give unnecessary details), described duplex straight-tooth conjugate crescent seal gear pump is connected with high-pressure mixing head 4 by pipeline, and high-pressure mixing head 4 is cast to material in the foam mold 7.Pipeline between duplex straight-tooth conjugate crescent seal gear pump and high-pressure mixing head 4 is provided with under meter 5.Described pump 3 adopts variable-frequency motor control.Set flow signal at control unit 6, the frequency of the variable-frequency motor of control unit 6 control pumps 3, thereby according to the target flow transferring raw material, simultaneously, under meter 5 sends to control unit 6 with flow signal, described control unit 6 passes the signal along to the frequency transformer 8 of the variable-frequency motor of pump 3, and described frequency transformer 8 is adjusted the output frequency of pump 3, thereby guarantees consistency of product.
Described foam stabilizer (or claiming suds-stabilizing agent) belongs to polyurethane surfactant; The dissolubility one that can increase each component plays a part emulsification foam material, stable foam and adjusting abscess.In the foam forming process, separating out of insoluble polyureas can destroy the stable of foam.A vital role of foam stabilizer is that polyureas is disperseed, and increases the consistency of polyureas and foam base plate.At present mostly the foam stabilizer that uses is the organic silicon modified by polyether polyurethane surfactant,, its primary structure is polysilane one olefin oxide segmented copolymer.The consumption of foam stabilizer is more big, and abscess is more thin, but might cause closed pore.In identical foaming system, suds-stabilizing agent generally need be higher than consumption in the high-density prescription at the consumption of low density foam.
Described pore-creating agent is the special polyurethane surfactant of a class, generally contains hydrophobicity and becomes group with hydrophilic segment, and its effect is the surface tension that reduces foam; Impel abscess to break, improve the percentage of open area of urethane foam, improve because of problems such as soft, semi-rigid that closed pore causes, the contractions of hard foam goods.General hard polyurethane foam is because the cross-linking density height, and the cell wall film toughness is big in the foaming, generally is the foam structure of closed pore, can open-celled rigid polyurethane foams processed but add pore-creating agent, be used for noise reduction, filtration etc.Early stage whiteruss, polyhutadiene, the methyl polysiloxanes etc. of using, the polyoxytrimethylene one ethylene oxide copolyether of the special chemical constitution of many employings, polyoxygenated alkene one polysiloxane copolymer etc. are as pore-creating agent at present.
Polyurethane surfactant (surfactant) refers to have fixing hydrophilic and oleophilic group, aligns at the surface energy of solution, and the material that surface tension is significantly descended.The molecular structure of polyurethane surfactant has amphipathic: an end is hydrophilic radical, and the other end is the hydrophobic group; Hydrophilic radical often is the group of polarity, as carboxylic acid, sulfonic acid, sulfuric acid, amino or amido and salt thereof, and also hydroxyl, amide group, ehter bond etc.; And the hydrophobic group is nonpolar hydrocarbon chain often, as 8 above hydrocarbon chains of carbon atom.Polyurethane surfactant is divided into ionic polyurethanes tensio-active agent and nonionic polyurethane tensio-active agent etc.
Thereby linking agent is to make the mutual bonding cross-linking of a plurality of thread-like molecules become the material of network structure at intermolecular bridging action of line style.The material that covalent linkage or ionic linkage form between promotion or telomerized polymer molecular chain.Linking agent has different calls in different industries.For example, be called " vulcanizing agent " in the rubber industry custom; Be called " solidifying agent ", " ripening agent ", " stiffening agent " at plastic industry; Be called " solidifying agent ", " stiffening agent " etc. at sizing agent or coating industry.Though more than address has difference, the chemical nature that reflects is identical.Polyurethane cross-linking agent uses TriMethylolPropane(TMP) more, Viscotrol C, and tetramethylolmethane, etc., generally be polyalcohols.
Nano-calcium carbonate is a kind of novel ultrafine solids powdered material that grows up the eighties in 20th century, and its granularity is between 0.01 ~ 0.1 μ m.Because the super-refinement of Nano particles of calcium carbonate, its crystalline structure and surface electronic structure change, and have produced the quantum size effect that ordinary calcium carbonate did not have, small-size effect, surface effects and macroscopic quantum effect.
A kind of method for preparing the high resilience moulded foam of nano-calcium carbonate filled polyurethane, finish according to following steps:
(1), according to the proportioning in the claim 1, polyether glycol 50kg, polymer polyatomic alcohol 25kg and nano-calcium carbonate 25kg are put into the high speed reactor, and high-speed stirring, stirring velocity are 130-150 commentaries on classics/min, churning time 30-45min makes and fully mixes;
(2), the material that mixes of step (1) changes in the low speed isothermal reaction still, add dimethyl aminoethyl ether 0.2kg, triethylene diamine 0.7kg, foam stabilizer 0.8kg, polyurethane surfactant 0.5kg, polyurethane cross-linking agent 1.5kg, pore-creating agent 1kg and water 3kg, keep 22-28 ℃ of temperature, stirring velocity is 35-45 commentaries on classics/min, and it is standby to stir;
(3), gained material in the step (2) is transferred in the storage tank 1 of urethane high-pressure foam, in control unit 6, set flow, the variable-frequency motor of control unit 6 control pumps 3 is adjusted frequency, under meter 5 is delivered to control unit 6 with flow signal, the variable-frequency motor of control unit 6 control pumps 3 is adjusted frequency, and realizes closed-loop control.The material that comes out from pump 3 arrives high-pressure mixing head 4, by high-pressure mixing head 4 material is cast in the foam mold 7, and foaming, the temperature of described foam mold is 50-60 ℃, dwell time 300-360s.
A kind of method for preparing the high resilience moulded foam of nano-calcium carbonate filled polyurethane, finish according to following steps:
(1), according to the proportioning in the claim 1, polyether glycol 70kg, polymer polyatomic alcohol 15kg and nano-calcium carbonate 15kg are put into the high speed reactor, and high-speed stirring, stirring velocity are 130-150 commentaries on classics/min, churning time 30-45min makes and fully mixes;
(2), the material that mixes of step (1) changes in the low speed isothermal reaction still, add dimethyl aminoethyl ether 0.3kg, triethylene diamine 1.0kg, foam stabilizer 1.2kg, polyurethane surfactant 0.8kg, polyurethane cross-linking agent 2kg, pore-creating agent 2kg and water 4kg, keep 22-28 ℃ of temperature, stirring velocity is 35-45 commentaries on classics/min, stirs standby;
(3), gained material in the step (2) is transferred in the storage tank 1 of urethane high-pressure foam, in control unit 6, set flow, the variable-frequency motor of control unit 6 control pumps 3 is adjusted frequency, under meter 5 is delivered to control unit 6 with flow signal, the variable-frequency motor of control unit 6 control pumps 3 is adjusted frequency, and realizes closed-loop control.The material that comes out from pump 3 arrives high-pressure mixing head 4, by high-pressure mixing head 4 material is cast in the foam mold 7, and foaming, the temperature of described foam mold is 50-60 ℃, dwell time 300-360s.
A kind of method for preparing the high resilience moulded foam of nano-calcium carbonate filled polyurethane, finish according to following steps:
(1), according to the proportioning in the claim 1, polyether glycol 60kg, polymer polyatomic alcohol 20kg and nano-calcium carbonate 20kg are put into the high speed reactor, and high-speed stirring, stirring velocity are 130-150 commentaries on classics/min, churning time 30-45min makes and fully mixes;
(2), the material that mixes of step (1) changes in the low speed isothermal reaction still, add dimethyl aminoethyl ether 0.25kg, triethylene diamine 0.8kg, foam stabilizer 1.0kg, polyurethane surfactant 0.6kg, polyurethane cross-linking agent 1.8kg, pore-creating agent 1.5kg and water 3.5kg, keep 22-28 ℃ of temperature, stirring velocity is 35-45 commentaries on classics/min, stirs standby;
(3), gained material in the step (2) is transferred in the storage tank 1 of urethane high-pressure foam, in control unit 6, set flow, the variable-frequency motor of control unit 6 control pumps 3 is adjusted frequency, under meter 5 is delivered to control unit 6 with flow signal, the variable-frequency motor of control unit 6 control pumps 3 is adjusted frequency, and realizes closed-loop control.The material that comes out from pump 3 arrives high-pressure mixing head 4, by high-pressure mixing head 4 material is cast in the foam mold 7, and foaming, the temperature of described foam mold is 50-60 ℃, dwell time 300-360s.
Claims (8)
1. high resilience moulded foam of nano-calcium carbonate filled polyurethane, it is characterized in that: the following starting material by parts by weight are made: polyether glycol 50-70 part, polymer polyatomic alcohol 15-25 part, nano-calcium carbonate 15-25 part, dimethyl aminoethyl ether 0.2-0.3 part, gel catalyst 0.7-1.0 part, foam stabilizer 0.8-1.2 part, polyurethane surfactant 0.5-0.8 part, linking agent 1.5-2 part, pore-creating agent 1-2 part, water 3-4 part.
2. according to the high resilience moulded foam of the described nano-calcium carbonate filled polyurethane of claim 1, it is characterized in that: described gel catalyst is triethylene diamine.
3. method for preparing the high resilience moulded foam of nano-calcium carbonate filled polyurethane is characterized in that: finish according to following steps:
(1), according to the proportioning in the claim 1, polyether glycol, polymer polyatomic alcohol and nano-calcium carbonate are put into the high speed reactor, high-speed stirring makes fully mixes;
(2), the material that mixes of step (1) changes in the low speed isothermal reaction still, adds dimethyl aminoethyl ether, gel catalyst, foam stabilizer, polyurethane surfactant, linking agent, pore-creating agent and water, keeps 22-28 ℃ of temperature, it is standby to stir;
(3), gained material in the step (2) is transferred to carries out high-pressure foam in the urethane high pressure foaming machine, described urethane high pressure foaming machine comprises foaming machine storage tank (1), outlet at foaming machine storage tank (1) arranges strainer (2), pump (3) is set in the outlet of described strainer (2), described pump (3) is the duplex straight-tooth conjugate crescent seal gear pump, described duplex straight-tooth conjugate crescent seal gear pump is connected with high-pressure mixing head (4) by pipeline, and the pipeline between duplex straight-tooth conjugate crescent seal gear pump and high-pressure mixing head (4) is provided with under meter (5); Material in the described step (2) is transferred to earlier in the storage tank (1) of high pressure foaming machine, passing through strainer (2) then filters, material is delivered to high-pressure mixing head (4) through pump (3) again, and material is cast to foaming in the foam mold (7) by high-pressure mixing head (4).
4. according to the described method for preparing the high resilience moulded foam of nano-calcium carbonate filled polyurethane of claim 3, it is characterized in that: described pump (3) adopts variable-frequency motor control.
5. according to the described method for preparing the high resilience moulded foam of nano-calcium carbonate filled polyurethane of claim 4, it is characterized in that: described high pressure foaming machine also comprises control unit (6), described under meter (5) passes to control unit (6) with flow signal, described control unit (6) passes the signal along to the frequency transformer (8) of the variable-frequency motor of pump (3), and described frequency transformer (8) is adjusted pump (3) output frequency.
6. according to the described method for preparing the high resilience moulded foam of nano-calcium carbonate filled polyurethane of claim 3, it is characterized in that: in the step (1), stirring velocity is 130-150 commentaries on classics/min, churning time 30-45min.
7. according to the described method for preparing the high resilience moulded foam of nano-calcium carbonate filled polyurethane of claim 3, it is characterized in that: in the described step (2), stirring velocity is 35-45 commentaries on classics/min.
8. according to the described method for preparing the high resilience moulded foam of nano-calcium carbonate filled polyurethane of claim 3, it is characterized in that: the temperature of described foam mold (7) is 50-60 ℃, dwell time 300-360s.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106397711A (en) * | 2016-09-22 | 2017-02-15 | 上海馨源新材料科技有限公司 | Low-density high-bearing sponge and manufacturing process |
| CN106750169A (en) * | 2016-12-21 | 2017-05-31 | 重庆德盈汽车零部件有限公司 | A kind of high resilience polyurethane foam and preparation method thereof |
| CN109293876A (en) * | 2018-10-08 | 2019-02-01 | 南通鸿图健康科技有限公司 | A kind of novel body building apparatus material and preparation method thereof |
| CN116063652A (en) * | 2023-01-10 | 2023-05-05 | 广东爱上新材料股份有限公司 | Foaming polyurethane coiled material for paving sports ground and preparation method thereof |
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| CN101319522A (en) * | 2008-06-06 | 2008-12-10 | 董海光 | Exterior wall heat preservation decorative lamination integration system and its production and mounting method |
| CN102140159A (en) * | 2010-11-26 | 2011-08-03 | 山东东大一诺威聚氨酯有限公司 | Environmental-friendly combination material for cold curing slow rebound polyurethane foam and preparation method thereof |
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| CN1201801A (en) * | 1997-05-05 | 1998-12-16 | 气体产品与化学公司 | Reactive catalyst compositions for improving water blown polyurethane foam performance |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106397711A (en) * | 2016-09-22 | 2017-02-15 | 上海馨源新材料科技有限公司 | Low-density high-bearing sponge and manufacturing process |
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| CN109293876A (en) * | 2018-10-08 | 2019-02-01 | 南通鸿图健康科技有限公司 | A kind of novel body building apparatus material and preparation method thereof |
| CN116063652A (en) * | 2023-01-10 | 2023-05-05 | 广东爱上新材料股份有限公司 | Foaming polyurethane coiled material for paving sports ground and preparation method thereof |
| CN116063652B (en) * | 2023-01-10 | 2023-08-11 | 广东爱上新材料股份有限公司 | Foaming polyurethane coiled material for paving sports ground and preparation method thereof |
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Application publication date: 20130821 |