WO2012106846A1 - 一种适用于平泡发泡工艺的mdi体系的非温感记忆海绵 - Google Patents

一种适用于平泡发泡工艺的mdi体系的非温感记忆海绵 Download PDF

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Publication number
WO2012106846A1
WO2012106846A1 PCT/CN2011/070935 CN2011070935W WO2012106846A1 WO 2012106846 A1 WO2012106846 A1 WO 2012106846A1 CN 2011070935 W CN2011070935 W CN 2011070935W WO 2012106846 A1 WO2012106846 A1 WO 2012106846A1
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polyol
polyether polyol
polyether
molecular weight
parts
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PCT/CN2011/070935
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English (en)
French (fr)
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倪张根
林涛
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江苏恒康家居科技有限公司
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Priority to CA2800374A priority Critical patent/CA2800374C/en
Priority to US13/824,031 priority patent/US9315613B2/en
Priority to PCT/CN2011/070935 priority patent/WO2012106846A1/zh
Priority to DE212011100115U priority patent/DE212011100115U1/de
Priority to CN201110109070.7A priority patent/CN102250311B/zh
Publication of WO2012106846A1 publication Critical patent/WO2012106846A1/zh
Priority to DKPA201370018A priority patent/DK178619B1/en
Priority to DKPA201370505A priority patent/DK201370505A/da

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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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1808—Catalysts containing secondary or tertiary amines or salts thereof having alkylene polyamine groups
    • 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
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
    • 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
    • C08G18/4825—Polyethers containing two hydroxy groups
    • 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
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • 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
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
    • 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
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • 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
    • C08G2110/0016—Foam properties semi-rigid
    • 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
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Definitions

  • the present invention relates to a non-temperature sensitive memory sponge of MDI system having a density of 40-70D, specifically a molecular weight of 700
  • a non-temperature sensitive memory sponge of MDI system prepared by adding a polyether polyol and an isocyanate as a main ingredient.
  • a non-temperature sensitive memory sponge for molding MDI system is introduced on the market.
  • the sponge is characterized by automatically adjusting the shape according to the shape and temperature of the body, and effectively suppressing the human body pressure to zero pressure. It counteracts the counter-power and provides the most average and real support.
  • the part that the body touches for a long time is in a state of no pressure, does not hinder the blood circulation and is not easy to cause fatigue and soreness.
  • the non-temperature memory foam is used in hospitals and can also provide patients with Maximum comfort, can effectively prevent the production of acne.
  • the superiority of non-temperature-sensitive memory sponge is difficult to compare with ordinary soft sponge.
  • the sponge has been manufactured by injection molding.
  • the main task of the present invention is to provide an MDI suitable for a flat foaming process.
  • the non-temperature sensitive memory sponge of the system is specifically a non-temperature sensitive memory sponge which is made of a MDI system with high tear strength and good elongation by adjusting the sponge formula, and can be applied to the flat foaming process.
  • the present invention is an MDI suitable for a flat foaming process.
  • the non-temperature-sensitive memory foam of the system is mainly prepared from a polyether polyol and a polymer polyol, and is prepared by adding three additives such as an isocyanate and a foaming agent, a pore former and a catalyst.
  • the polyether polyol is a molecular weight.
  • the polymer polyol is a highly reactive graft polyether
  • the isocyanate is a modified polyphenylmethane diisocyanate, characterized in that the polyether polyol has an increased molecular weight of 4,800 a polyoxypropylene trihydroxy ether in which the polyol chain extender is added; among the above components, the total mass of the polyether polyol and the polymer polyol is 100 parts, and the foaming agent is 1.5-3
  • the mass fraction and the isocyanate mass fraction are determined according to the above all hydroxyl value component multiplied by the corresponding hydroxyl value of each component and then multiplied by a constant of 0.155, plus a foaming agent containing no hydroxyl value, the calculation of the foaming agent Multiply the constant by the blowing agent 9.665; finally multiplying the total number of the above isoculated by the hardness index of the final isocyanate mass.
  • polyoxypropylene trihydroxy ether having a molecular weight of 4,800 is added in an amount of 60-80% by weight based on the weight of the main polyol.
  • the polyol chain extender is used in an amount of 2 to 5 parts by weight based on the weight of the main polyol.
  • the polyol chain extender is a polyether polyol having a molecular weight of 100, such as a polyoxyethylene glycol.
  • the production principle of the invention is: replacing the traditional dangerous chemicals with environmentally friendly MDI.
  • TDI production of gas sensitive sponge is environmentally friendly, but MDI
  • the air-sensing sponge that is emitted generally has a relatively poor tearing strength, so only the mold can be made into a small sponge block, which cannot satisfy a large-area sponge such as a mattress.
  • the tear strength and molecular weight were 4,800.
  • the polyether polyol is related to the fact that the large-scale foaming production cannot be achieved because the original mold production formula is placed in the flat foaming process, and the internal structure of the sponge obtained is hollow, similar to the column structure, and the link is not Ok, it's easy to be torn.
  • the present invention is improved in the conventional mold production formula, a certain amount of chain extender is added, and the relevant ratio of other components is adjusted, so that the internal structure of the sponge is expanded by the large area of the foam.
  • the shape structure becomes a mesh structure, which increases the link point of the internal structure of the sponge, thereby achieving the process requirement for large-area overall production suitable for flat foaming.
  • the internal structure of the sponge is a mesh shape, and when used, the heat of the human body can be rapidly dispersed along the mesh structure of the sponge to form The 'capillary' phenomenon, which causes the inside of the sponge to not collect external heat, improve permeability and provide better comfort.
  • the advantage of the invention is that the MDI using the above formula
  • the sponge of the system which uses the large-molecular-weight polyether polyol which was originally used as a pore-forming agent as a main material and supplemented with a chain extender, can use a flat foaming production line to produce a large sponge, breaking the original MDI.
  • the system's gas-sensing sponge can only be used to make small-area sponge production limitations.
  • the above formula is used to realize the assembly line operation, which has the advantages of quick discharge and high efficiency, and the general MDI
  • the speed of the system is improved by at least 100 compared to the injection molding of the system. It is important that the line does not require a sponge of one shape to be equipped with a mold, and it is only necessary to cut the entire sponge into a desired shape by using a cutter, thereby reducing unnecessary mold costs.
  • the selection of the non-temperature sensitive memory sponge of the MDI system of the density 40-70D of the present invention is as follows:
  • the preparation component and the weight ratio are as follows: 100 parts of the polyol, for example, isocyanate is 40--70 parts, the pore former is 1.4--2.5 parts, and the catalyst is 0.1--0.4. Parts, main foaming agent water 1.5--2.5 parts, auxiliary blowing agent dichloromethane 0-10; polyol chain extender 2-5 parts.
  • the polyether polyol is the following parts by weight of a polyether polyol: a polyether polyol having a molecular weight of 700: 10-20 parts; 4800 polyether polyol: 60-80 parts, polymer polyol: 5-20 parts.
  • the above polyol chain extender is a polyoxyethylene diol of a polyether polyol having a molecular weight of 100.
  • each material is placed in the respective containers in proportion, and then the temperature of the whole raw material is maintained at 22-25 °C. Subsequent production at the temperature.
  • the materials are mixed next.
  • the steps of material mixing are as follows: the above independent containers are connected to the mixer through the pipeline, and the metering rods and the electromagnetic valves are arranged at the plurality of pipeline mouths; when the materials flow out, the electromagnetic valve is opened, and the flow rate is accurately controlled by the measuring rods. Flow into the mixer and stir in the mixer until the solution is well mixed.
  • the mixed solution is sprayed to the distributor through a spray nozzle communicating with the mixer, and the solution is The flow rate of 150-320kg/min is evenly distributed to the crawler in the line oven.
  • the temperature in the oven is 30-40 °C; the mixed solution is 0.05-0.09 m in the oven.
  • the speed of the second is continuously foamed, the crawler belt is continuously moved, and the foamed portion is moved forward to make room for the subsequent foamed raw materials.
  • baffles are provided on both sides of the line crawler, and the baffle determines the width of the sponge.
  • the height of the sponge is determined by the density of the sponge, the speed of the crawler and the flow rate of the mixed solution.
  • the following materials were selected as the sponge raw material: 100 parts by weight of the polyol, and modified polyphenylmethane diisocyanate was 61.
  • the parts by weight of the polysiloxane polyether copolymer pore-forming agent are 2 parts by weight, the catalyst of the triethylenediamine solution is 0.2 parts by weight, the main blowing agent water is 2.4 parts by weight, and the auxiliary blowing agent methylene chloride is 5
  • the above 100 parts of the polyol are composed of the following four components in the following proportions: 70 parts Mn4800 polyether polyol, 20 parts Mn700 polyether polyol, 10 parts polymer polyol.
  • the above polyether polyol is mixed with a plurality of high molecular weight polyether polyols.
  • the molecular weight is 4,800.
  • the polyether polyol is specifically polyoxypropylene trihydroxy ether; the polyether polyol having a molecular weight of 700 is specifically polyoxypropylene glycerol, and the polymer polyol is specifically a highly reactive graft polyether.
  • the above materials are mixed as described above at a temperature of 22 to 25 ° C to form a mixed solution, and the mixed solution is passed through a distributor at 215 kg.
  • the flow rate of /s is distributed in an oven with a width of 2 meters.
  • the crawler moves forward at a speed of 3.5 meters at a temperature of 30-40 ° C.
  • the density is 40D and the height is 78cm. Continuity of large sponges.
  • the production line adopts the flat foaming process, and the support degree is consistent with the support degree of the ordinary sponge, and the sponge body does not collapse.
  • the advantage is that the speed is increased by at least 100 compared to previous injection molding.
  • the subsequent molding of the product can be shaped by special-shaped cutting, and the shape of the molding is ever-changing, which can be any shape product that we can imagine. Since the above-mentioned forming adopts a cutting method, not only the raw materials are saved, but also a large amount of mold costs are reduced, and the economic benefits are remarkable.
  • the following materials were selected as the sponge raw material: 100 parts of the polyol was taken as an example, and the modified polyphenylmethane diisocyanate was 53.
  • the polysiloxane polyether copolymer pore-forming agent is 2, the triethylene diamine solution catalyst is 0.18 parts, the main blowing agent water is 2.3 parts, the auxiliary blowing agent dichloromethane is 2 parts, and the molecular weight is 100 parts.
  • Polyether polyol chain extender 3 parts of polyoxyethylene glycol.
  • the above 100 parts of the polyol are composed of the following four components in the following proportions: 75 parts Mn4800 polyether polyol, 15 parts Mn700 polyether polyol, 10 parts polymer polyol.
  • the above polyether polyol is mixed with a plurality of high molecular weight polyether polyols.
  • the molecular weight is 4,800.
  • the polyether polyol is specifically polyoxypropylene trihydroxy ether; the polyether polyol having a molecular weight of 700 is specifically polyoxypropylene glycerol, and the polymer polyol is specifically a highly reactive graft polyether.
  • the above materials are mixed as described above at a temperature of 22 to 25 ° C to form a mixed solution, and the mixed solution is passed through a distributor to 250.
  • the flow rate in kg/min is distributed in an oven with a width of 2 m at a temperature of 30-40 ° C.
  • the crawler is 3.5 m in the oven.
  • the forward speed is shifted, that is, the continuous bulk sponge with a density of 46D and a height of 78cm is produced by the production process of the flat foaming process.
  • Test items unit Sample test value Recovery time S 10.3 75% compression set % 48.9 Rebound rate % 10 Tensile Strength KPa 51 Elongation % 258.1 Tear strength N/cm 1.4 Odor level level 3.0 Rate of change of tensile strength after dry heat aging % 16.2 Rate of change of tensile strength after damp heat aging % 3.2 65% 25% indentation ratio - 2.6 40% indentation hardness loss value after repeated indentation fatigue under constant load % 4.0 Temperature and humidity sensitivity - 2 . 2
  • the following materials were selected as the sponge raw material: 100 parts of the polyol, for example, the modified polyphenylmethane diisocyanate was 50.
  • the polysiloxane polyether copolymer pore-forming agent is 1.8
  • the triethylene diamine solution catalyst is 0.18 parts
  • the main foaming agent water is 2.3 parts
  • the polyether polyol chain extender polyoxyethylene glycol 2 parts .
  • the above 100 parts of the polyol are composed of the following four components in the following proportions: 80 parts Mn4800 polyether polyol, 10 parts Mn700 polyether polyol, polymer polyol 10 parts.
  • the above polyether polyol is mixed with a plurality of high molecular weight polyether polyols.
  • the molecular weight is 4,800.
  • the polyether polyol is specifically polyoxypropylene trihydroxy ether; the polyether polyol having a molecular weight of 700 is specifically polyoxypropylene glycerol, and the polymer polyol is specifically a highly reactive graft polyether.
  • the above materials are mixed as described above at a temperature of 22 to 25 ° C to form a mixed solution, and the mixed solution is passed through a distributor to 250.
  • the flow rate in kg/min is distributed in an oven with a width of 2 m at a temperature of 30-40 ° C.
  • the crawler is 3.3 m in the oven.
  • the speed of the forward movement that is, the production line of the flat foaming process, produces a continuous bulk sponge with a density of 50D and a height of 76cm.
  • Test items unit Sample test value Recovery time S 12 75% compression set % 55.3 Rebound rate % 10
  • Temperature and humidity sensitivity - 2 1
  • the following materials were selected as the sponge raw material: 100 parts of the polyol, for example, the modified polyphenylmethane diisocyanate was 52.
  • the polysiloxane polyether copolymer pore-forming agent is 1.6
  • the triethylene diamine solution catalyst is 0.16
  • the main foaming agent water is 2.1 parts
  • the polyether polyol chain extender is 5 parts.
  • the polyol is composed of the following four components in the following proportions: 60 parts of Mn4800 polyether polyol, 20 parts of Mn700 polyether polyol, and 20 parts of polymer polyol.
  • the above polyether polyol is mixed with a plurality of high molecular weight polyether polyols.
  • the molecular weight is 4,800.
  • the polyether polyol is specifically polyoxypropylene trihydroxy ether; the polyether polyol having a molecular weight of 700 is specifically polyoxypropylene glycerol, and the polymer polyol is specifically a highly reactive graft polyether.
  • the above materials are mixed as described above at a temperature of 22 to 25 ° C to form a mixed solution, and the mixed solution is passed through a distributor to 285
  • the flow rate of kilograms per minute is distributed in an oven with a width of 2 meters.
  • the crawler moves forward at a speed of 3.5 meters at a temperature of 30-40 ° C.
  • the density is 55D and the height is 74cm. Continuity of large sponges.
  • Test items unit Sample test value Recovery time S 11 75% compression set % 60.2 Rebound rate % 10 Tensile Strength KPa 43.3 Elongation % 247.3 Tear strength N/cm 1.2 Odor level level 3.0 Rate of change of tensile strength after dry heat aging % 16.2 Rate of change of tensile strength after damp heat aging % 3.2 65% 25% indentation ratio - 2.6 40% indentation hardness loss value after repeated indentation fatigue under constant load % 5.0 Temperature and humidity sensitivity - 2 . 2

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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)

Description

一种适用于平泡发泡工艺的 MDI 体系的非温感记忆海绵
技术领域
本发明涉及一种密度在 40-70D 的 MDI 体系的非温感记忆海绵，具体是一种主要由分子量为 700 的聚醚多元醇和异氰酸酯作主料，添加助剂制得的 MDI 体系的非温感记忆海绵。
背景技术
随着生活水平的提高，人们对家居的舒适性要求也越来越高。普通软质海绵制品一向以柔软、有弹性而被家具商大量采纳。但是，在使用过程中，普通软质海绵制品存在对人体血管回弹压力大，夏天闷热、冬天质地发硬，舒适性较差的缺点，使得普通软质海绵的应用范畴受到局限。
为了弥补普通软质海绵的不足，目前市场上推出一种模塑 MDI 体系的非温感记忆海绵，该海绵的特点为根据身体的形状和温度自动调整形状，有效把人体压力化解为零压，抵消反动力，提供最平均、真实的支撑，使身体长时间接触的部位处于无压力状态，不阻碍血液循环及不易产生疲劳及酸痛，非温感记忆海绵用于医院中，还可为病人提供最大限度的舒适感，能有效地防止褥疮的产生。非温感记忆海绵的优越性是普通软质海绵难以媲美的，但是，该海绵的制造一直都是采用注塑工艺，以模具为载体，一次只可以制作一块体积不大于 0.5m3 的海绵，仅适用制作诸如枕头、玩具类的小制品，该生产工艺严重阻碍了非温感记忆海绵海绵应用领域的进一步扩大，不适应如床垫等大件海绵的制作，且一模一模地制作，不适合大规模生产，效率低下。
发明内容
本发明的主要任务在于提供一种适用于平泡发泡工艺的 MDI 体系的非温感记忆海绵，具体是一种通过海绵体配方的调整，制造出撕裂强度高、拉伸率较好的 MDI 体系的非温感记忆海绵，能适用于平泡发泡工艺。
为了解决以上技术问题，本发明的一种适用于平泡发泡工艺的 MDI 体系的非温感记忆海绵，主要由聚醚多元醇和聚合物多元醇为主料，加入异氰酸酯和发泡剂、整孔剂、催化剂这三种助剂制得，所述聚醚多元醇为分子量为 700 的聚氧丙烯甘油醇，所述聚合物多元醇为高活性接枝聚醚，所述异氰酸酯为改性的多苯基甲烷二异氰酸酯，其特征在于：所述聚醚多元醇中增加分子量为 4800 的聚氧丙烯三羟基醚，所述助剂中增加多元醇链延长剂；在上述成分中，聚醚多元醇和聚合物多元醇的总质量分为 100 份，发泡剂则为 1.5-3 质量分，异氰酸酯质量份的确定是根据上述所有含羟值组分乘以各个组分对应的羟值后再乘以常数 0.155 ，加上不含羟值的发泡剂，该发泡剂的计算为发泡剂乘以常数 9.665 ；最后以上述总数乘以硬度指数的最终的异氰酸酯质量分。
进一步地，所述分子量为 4800 的聚氧丙烯三羟基醚加入量占主料多元醇重量份的 60-80% ；所述多元醇链延长剂所用重量份为占主料多元醇重量份的 2-5 份。
进一步地，所述多元醇链延长剂为分子量为 100 的聚醚多元醇，如聚氧乙烯二元醇。
本发明的制作原理是：用环保型的 MDI 代替传统的危险化学物品 TDI 生产气感海绵是环保的，但 MDI 发出来的气感海绵一般撕裂强度比较差，因此只能模具制作成小海绵块，对如床垫之类的大面积整体海绵无法满足。在实验中，得到撕裂强度与分子量为 4800 的聚醚多元醇有关，之所以不能实现大面积的发泡生产，是因为原模具生产的配方在置于平泡工艺中，所得到的海绵内部结构呈空心的、类似于柱结构，链接不好，容易被撕裂。针对这一现象，本发明在传统的模具生产配方中加以改进，加入一定量的链延长剂，并调整其他组分的相关配比，使得大面积平泡发泡时，海绵的内部结构由柱形结构变为网状结构，增加海绵内部结构的链接点，从而达到适合平泡发泡的大面积整体生产的工艺要求。
在本发明中，由于配方的改进，海绵的内部结构为网状，使用时，人体的热量便能顺着海绵的网状结构快速分散，形成 ' 毛细 ' 现象，该现象使得海绵内部不会聚集外界的热量，通透性提高，舒适感更佳。
本发明的优点在于：采用上述配方的 MDI 体系的海绵，其将原来做整孔剂的大分子量聚醚多元醇作为主料、辅以链延长剂，就可以采用平泡发泡流水线进行大块海绵的生产，打破了原来 MDI 体系气感海绵只能用模具进行小面积海绵体生产的局限。
采用上述配方实现流水线作业，具有出料快、效率高的优点，与一般的 MDI 体系气感海绵的注塑成型相比，速度提高了至少 100 倍；重要的是，该流水线不需要一种形状的海绵配备一个模具，只需要将整块海绵生产好后用切割刀切割成需要的形状即可，减少了不必要的模具费用。
具体实施方式
本发明的一种密度 40-70D 的 MDI 体系非温感记忆海绵的选料为以下成分及配比 : 所述制作组分及重量份配比如下 : 以多元醇 100 份为例，异氰酸酯为 40--70 份，整孔剂为 1.4--2.5 份，催化剂为 0.1--0.4 份，主要发泡剂水 1.5--2.5 份，辅助发泡剂二氯甲烷 0-10 ；多元醇链延长剂 2-5 份。
所述聚醚多元醇为以下重量份的聚醚多元醇：分子量为 700 的聚醚多元醇： 10-20 份；分子量为 4800 的聚醚多元醇： 60-80 份，聚合物多元醇： 5-20 份。
上述多元醇链延长剂为分子量为 100 的聚醚多元醇的聚氧乙烯二元醇。
将上述物料选好后，将每种物料按比例单独置于各自的容器内，然后将整个原料的温度保持在 22-25 ℃ 的温度下进行后续制作。
物料单独配置后，接下来进行物料混合。物料混合的步骤为：将以上独立的容器通过管道均连通至混合器内，在若干管道口处均设有计量棒和电磁阀；物料流出时，打开电磁阀，通过计量棒精确控制流量，物料流至混合器内，在混合器中进行搅拌至溶液混合均匀。混合溶液通过与混合器连通的喷射嘴喷射至分布器，由分布器将溶液以 150-320kg/ 分的流速均匀分布至流水线烘箱内的履带上，烘箱中的温度为 30-40℃ ；混合溶液在烘箱内以 0.05-0.09米/ 秒的速度进行连续发泡，履带不断移动，将发泡好的部分向前推移，给后续发泡的原料腾出空间。
该工艺中，流水线履带的两侧设有挡板，该挡板决定海绵的宽度，海绵的高度由海绵的密度、履带的传速和混合溶液的流量决定的。
实施例 1
选以下物料作为海绵原料：以多元醇 100 重量份为例，改性的多苯基甲烷二异氰酸酯为 61 重量份，聚硅氧烷聚醚共聚物整孔剂为 2 重量份，三乙烯二胺溶液催化剂为 0.2 重量份，主要发泡剂水 2.4 重量份，辅助发泡剂二氯甲烷为 5 重量份，分子量为 100 的聚醚多元醇链延长剂：聚氧乙烯二元醇为 4 重量份。
上述的 100 份多元醇由以下四种成分按以下比例构成： 70 份 Mn4800 聚醚多元醇、 20 份 Mn700 聚醚多元醇、 10 份聚合物多元醇构成。
且上述聚醚多元醇为多种高分子量聚醚多元醇混合。在本实施例中，分子量为 4800 的聚醚多元醇具体为聚氧丙烯三羟基醚；分子量为 700 的聚醚多元醇具体为聚氧丙烯甘油醇、聚合物多元醇具体为高活性接枝聚醚。
将上述原料在 22-25℃ 的温度下进行上述的混合，形成混合溶液，并将混合后的溶液通过分布器以 215kg /s 的流量分布至宽度为 2 米 的烘箱内，在温度为 30-40℃ 烘箱内履带以 3.5 米 的传速向前移动，生成密度为 40D ，高度为 78cm 的连续性大块海绵。
采用该工艺生产的海绵，按照 GB/T24451-2009 《慢回弹软质聚氨酯泡沫塑料》的标准进行检测（附：由于本产品还没有检测标准，故暂采用该标准检测），检测结果为：
检测项目 单位 样品检验值
复原时间 S 10.3
75% 压缩永久变形 % 64.9
回弹率 % 10
拉伸强度 KPa 43.3
伸长率 % 258.1
撕裂强度 N/cm 1.01
气味等级 级 3.0
干热老化后拉伸强度变化率 % 16.2
湿热老化后拉伸强度变化率 % 3.2
65%25% 压陷比 - 2.6
恒定负荷反复压陷疲劳后 40% 压陷硬度损失值 % 4.0
温湿度敏感性 - 2 ． 2
总结上表可得，本实施例的产品撕裂强度等参数在上述条件下，基本接近 GB/T24451-2009 《慢回弹软质聚氨酯泡沫塑料》的标准，生产的产品为合格产品。
采用平泡发泡工艺的流水线生产方式，其支承度与普通海绵的支撑度趋于一致，海绵本体不下塌。优点在于：与先前的注塑成型相比，速度至少提高了 100 倍，其产品的后续成型可以采用异形切割成型，其成型的形状千变万化，可以是我们所能想象的任何形状的产品。由于上述成型采用的是切割方式，不但节省了原料，更减少了大量的模具费，其经济效益显著。
实施例 2
选以下物料作为海绵原料：以多元醇 100 份为例，改性的多苯基甲烷二异氰酸酯为 53 份，聚硅氧烷聚醚共聚物整孔剂为 2 ，三乙烯二胺溶液催化剂为 0.18 份，主要发泡剂水 2.3 份，辅助发泡剂二氯甲烷为 2 份；分子量为 100 的聚醚多元醇链延长剂：聚氧乙烯二元醇 3 份。上述的 100 份多元醇由以下四种成分按以下比例构成： 75 份 Mn4800 聚醚多元醇、 15 份 Mn700 聚醚多元醇、 10 份聚合物多元醇。
且上述聚醚多元醇为多种高分子量聚醚多元醇混合。在本实施例中，分子量为 4800 的聚醚多元醇具体为聚氧丙烯三羟基醚；分子量为 700 的聚醚多元醇具体为聚氧丙烯甘油醇、聚合物多元醇具体为高活性接枝聚醚。
将上述原料在 22-25℃ 的温度下进行上述的混合，形成混合溶液，并将混合后的溶液通过分布器以 250 公斤 / 分的流量分布至宽度为 2 米 的烘箱内，在温度为 30-40℃ 烘箱内履带以 3.5 米 的传速向前移动，即采用平泡发泡工艺的流水线生产方式生成密度为 46D 、高度为 78cm 的连续性大块海绵。
检测项目 单位 样品检验值
复原时间 S 10.3
75% 压缩永久变形 % 48.9
回弹率 % 10
拉伸强度 KPa 51
伸长率 % 258.1
撕裂强度 N/cm 1.4
气味等级 级 3.0
干热老化后拉伸强度变化率 % 16.2
湿热老化后拉伸强度变化率 % 3.2
65%25% 压陷比 - 2.6
恒定负荷反复压陷疲劳后 40% 压陷硬度损失值 % 4.0
温湿度敏感性 - 2 ． 2
总结上表可得，本实施例的产品撕裂强度等参数在上述条件下，基本接近 GB/T24451-2009 《慢回弹软质聚氨酯泡沫塑料》的标准，生产的产品为合格产品。
实施例 3
选以下物料作为海绵原料：以多元醇 100 份为例，改性的多苯基甲烷二异氰酸酯为 50 份，聚硅氧烷聚醚共聚物整孔剂为 1.8 ，三乙烯二胺溶液催化剂为 0.18 份，主要发泡剂水 2.3 份，聚醚多元醇链延长剂：聚氧乙烯二元醇 2 份。
上述的 100 份多元醇由以下四种成分按以下比例构成： 80 份 Mn4800 聚醚多元醇、 10 份 Mn700 聚醚多元醇、聚合物多元醇 10 份。
且上述聚醚多元醇为多种高分子量聚醚多元醇混合。在本实施例中，分子量为 4800 的聚醚多元醇具体为聚氧丙烯三羟基醚；分子量为 700 的聚醚多元醇具体为聚氧丙烯甘油醇、聚合物多元醇具体为高活性接枝聚醚。
将上述原料在 22-25℃ 的温度下进行上述的混合，形成混合溶液，并将混合后的溶液通过分布器以 250 公斤 / 分的流量分布至宽度为 2 米 的烘箱内，在温度为 30-40℃ 烘箱内履带以 3.3 米 的传速向前移动，即采用平泡发泡工艺的流水线生产方式生成密度为 50D 、高度为 76cm 连续性大块海绵。
采用该工艺生产的海绵，按照 GB/T24451-2009 《慢回弹软质聚氨酯泡沫塑料》的标准进行检测（附：由于本产品还没有检测标准，故暂采用该标准检测），检测结果为：
检测项目 单位 样品检验值
复原时间 S 12
75% 压缩永久变形 % 55.3
回弹率 % 10
拉伸强度 KPa 50
伸长率 % 258.1
撕裂强度 N/cm 1.08
气味等级 级 3.0
干热老化后拉伸强度变化率 % 16.2
湿热老化后拉伸强度变化率 % 3.2
65%25% 压陷比 - 2.6
恒定负荷反复压陷疲劳后 40% 压陷硬度损失值 % 4.0
温湿度敏感性 - 2 ． 1
总结上表可得，本实施例的产品撕裂强度等参数在上述条件下，基本接近 GB/T24451-2009 《慢回弹软质聚氨酯泡沫塑料》的标准，生产的产品为合格产品。
实施例 4
选以下物料作为海绵原料：以多元醇 100 份为例，改性的多苯基甲烷二异氰酸酯为 52 份，聚硅氧烷聚醚共聚物整孔剂为 1.6 ，三乙烯二胺溶液催化剂为 0.16 份，主要发泡剂水 2.1 份；聚醚多元醇链延长剂 5 份。上述的 100 份多元醇由以下四种成分按以下比例构成： 60 份 Mn4800 聚醚多元醇、 20 份 Mn700 聚醚多元醇、聚合物多元醇 20 份。
且上述聚醚多元醇为多种高分子量聚醚多元醇混合。在本实施例中，分子量为 4800 的聚醚多元醇具体为聚氧丙烯三羟基醚；分子量为 700 的聚醚多元醇具体为聚氧丙烯甘油醇、聚合物多元醇具体为高活性接枝聚醚。
将上述原料在 22-25℃ 的温度下进行上述的混合，形成混合溶液，并将混合后的溶液通过分布器以 285 公斤 / 分的流量分布至宽度为 2 米 的烘箱内，在温度为 30-40℃ 烘箱内履带以 3.5 米 的传速向前移动，生成密度为 55D 、高度为 74cm 的连续性大块海绵。
采用该工艺生产的海绵，按照 GB/T24451-2009 《慢回弹软质聚氨酯泡沫塑料》的标准进行检测（附：由于本产品还没有检测标准，故暂采用该标准检测），检测结果为：
检测项目 单位 样品检验值
复原时间 S 11
75% 压缩永久变形 % 60.2
回弹率 % 10
拉伸强度 KPa 43.3
伸长率 % 247.3
撕裂强度 N/cm 1.2
气味等级 级 3.0
干热老化后拉伸强度变化率 % 16.2
湿热老化后拉伸强度变化率 % 3.2
65%25% 压陷比 - 2.6
恒定负荷反复压陷疲劳后 40% 压陷硬度损失值 % 5.0
温湿度敏感性 - 2 ． 2
总结上表可得，本实施例的产品撕裂强度等参数在上述条件下，基本接近 GB/T24451-2009 《慢回弹软质聚氨酯泡沫塑料》的标准，生产的产品为合格产品。

Claims (1)

  1. 1 、一种适用于平泡发泡工艺的 MDI 体系的非温感记忆海绵，主要由聚醚多元醇和聚合物多元醇为主料，加入异氰酸酯和发泡剂、整孔剂、催化剂这三种助剂制得，所述聚醚多元醇为分子量为 700 的聚氧丙烯甘油醇，所述聚合物多元醇为高活性接枝聚醚，所述异氰酸酯改性的多苯基甲烷二异氰酸酯，其特征在于：所述聚醚多元醇中增加分子量为 4800 的聚氧丙烯三羟基醚，所述助剂中增加多元醇链延长剂；在上述成分中，聚醚多元醇和聚合物多元醇的总质量分为 100 份，发泡剂则为 1.5-3 质量分，异氰酸酯质量份的确定是根据以下方式：将上述所有含羟值组分乘以各个组分对应的羟值后再乘以常数 0.155 加上，不含羟值的发泡剂乘以常数 9.665 的值；最后以上述总数乘以硬度指数得最终的异氰酸酯质量分。
    2 、根据全要求 1 所述的一种适用于平泡发泡工艺的 MDI 体系的非温感记忆海绵，其特征在于：所述分子量为 4800 的聚氧丙烯三羟基醚加入量占主料多元醇重量份的 60-80% ；所述多元醇链延长剂所用重量份为占主料多元醇重量份的 2-5 份。
    3 、根据全要求 1 所述的一种适用于平泡发泡工艺的 MDI 体系的非温感记忆海绵，其特征在于：所述多元醇链延长剂为分子量为 100 的聚醚多元醇，如聚氧乙烯二元醇。
PCT/CN2011/070935 2011-02-11 2011-02-11 一种适用于平泡发泡工艺的mdi体系的非温感记忆海绵 WO2012106846A1 (zh)

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