TW564253B - Hard polyurethane open-pore foamed body composition and manufacturing method thereof - Google Patents

Abstract

This invention provides a method for manufacturing a hard polyurethane open-pore foamed body; because of the good pore openness and hardness, gases in the foamed body can be removed by vacuum pumping method to reduce the thermal conductivity and the article made thereof is not deformed easily, which makes the material suitable to be used as a heat insulation material in a vacuum heat insulation bag. The formulation disclosed in the invention is suitable to be cured and foamed under ambient temperature and the foaming method utilizes carbon dioxide released from reaction of water and isocyanate functional group in the formulation without using organic chlorofluorocarbon compounds which are harmful to environment.

Description

564253

^ Jl_89i〇5188 V. Description of the invention (1) Background of the invention The foam is heat conduction and heat treatment, and the problem that the closed medium will destroy is unsolved. The cold-curing rigid foam body has the applicant's application. This cold-set is prepared and used as a way to be incorporated into the literature from Takeda TS-470 of Japan and added to the company's decision. Square vacuum insulation material Traditionally used as a heat insulation material, rigid polyurethane uses a foaming agent (refrigerant) to form a foam structure. In order to reduce the heat flow of gas flow, it is necessary to find an appropriate refrigerant pore structure with a small thermal conductivity. Reduce gas convection heat transfer. However, recently, the ozone layer in the old cold air was found, and the new refrigerant has many complications. Therefore, polyurethane foams that are completely free of refrigerant and water-foamed have been gradually applied to vacuum insulation materials. It has fine cells and good openness, and has good thermal insulation effect. In the approved new-type patent No. 108173, a high-barrier bag made of rigid polyurethane foam is a vacuum insulation sheet, the contents of which are incorporated herein by reference. . The cold-curing rigid polyurethane foaming system was purchased by the company with the code “ACTOOL VW-75” and the code “TAKENATEE foaming solution” after being emulsified and foamed. However, the inventor did not disclose the manufacturing process of the above-mentioned products of the company, and deliberately protected the secrets of the manufacturing process of the above-mentioned products. A method for formulating an open-cell foam of ethyl acetate, which has fine cells and good open-cell properties, and is suitable as material 0. Summary of the invention-a rigid polyurethane open-cell foam prepared in accordance with the present invention The composition contains liquid A and liquid B, where liquid A contains ...

Page 5 564253 Case No. 89105188 V. Description of the invention (2) 100 parts by weight of a polyether polyol having 3 to 5 hydroxyl functional groups and a hydroxyl value of 300 to 700 mgKOH / g; 1 to 3.6 parts by weight of non-hydrolyzed Polysiloxane surfactant; 0.2 to 3 parts by weight of tertiary amine catalyst; 0.2 to 2.6 parts by weight of water; and 0.2 to 2.4 parts by weight of carbon atoms c2-C8 polyol chain extender And liquid B contains polyisocyanate, wherein the weight ratio of liquid B to liquid A is between 0.7 and 1.2. Optionally, the liquid A of the present invention may further contain 0.4 to 1% by weight of a cross-linking agent, such as diethanolamine, glycerol, and triethanolamine. Suitable polyisocyanates include polyfunctional groups having 2 to 3 Isocyanates such as diphenylmethane diisocyanate (MD 丨), tolyl dimethyl dicyanate (TDI), hexamethylene diisocyanate, isophorone diisocyanate, dibenzobenzenediisocyanate, triphenylbenzene Methyl triisocyanates and their mixtures. Preferably, it is an isocyanate mixture having an MD-based isocyanate functional group of about 2.7. Suitable C2-C8 polyol chain extenders are, for example, propylene glycol or ethylene glycol. The tertiary amine catalyst suitable for use in the present invention may be any tertiary amine catalyst known in the art of polyurethane, and is preferably 2,2'-dimorphofluordiethyl ether [2, 2 '-Dimorpholinodiethylether, (herein referred to as DMDEE)], Triethylenediamine (herein referred to as TEDA)], 33% TEDA dissolved in dipropylene glycol (herein referred to as TD-33) And pentamethyldiethylenetriamine, (herein referred to as,

564253 _ Prime No. 89105188 / 〇 Di: t: _ 5. Description of the invention (3) PMDETA)] ° Polyether polyols suitable for the present invention are composed of polyfunctional groups such as glycerol, sucrose, hexadecanol and the like Polymers of alkylene oxides (such as propylene oxide and ethylene oxide) are, for example, polyether polyols purchased from Dow Chemical Company under the code VRANOLL360 and VORANOL490. A method suitable for manufacturing the rigid polyurethane open-cell foam of the present invention comprises the following steps: a) mixing 100 parts by weight of 3 to 5 hydroxyl functional groups and a hydroxyl value of 3 to 70 mgKOH / g polyether polyol, 1 to 3.6 parts by weight of a non-hydrolyzable polysiloxane surfactant, 0.2 to 3 parts by weight of a tertiary amine catalyst, 0.2 to 2. 6 4 parts by weight of water 'and 0.2 to 2.4 parts by weight of carbon atoms C2-C8 polyol chain extender to prepare a liquid A; b) preheating the liquid A in step a) to keep it at The temperature of 25-45 ° C; c) Preheating the B liquid of polyisocyanate to keep it at a temperature of 25-45 ° C; d) Preheating the liquids A and B with B and A The weight ratio of the liquid is 0.7 ~ 1 · 2, and the mixture is quickly added and mixed, and then the obtained mixture is injected into a mold at a temperature of 35-5 5 t and the temperature is higher than the mixture of the A liquid and the B liquid. Curing and foaming; and, e) removing a polyurethane open-cell foam from the mold. φ Preferably, in the step d), the mixture of the a liquid and the B liquid in the mold is cured and foamed for 2 minutes to 10 minutes. DETAILED DESCRIPTION OF THE INVENTION The present invention discloses a cold-curing rigid polyurethane (PU) foam that is completely foamed with water without using a refrigerant at all.

Page 7 564253 _____ Case No. 891Q5188_ ^ Yan Xi Yue Guang ^ __ Amendment ___ V. Description of the invention (4) Holes and good opening properties, the hole diameter is 0.08mm or less, and the opening ratio is 90 % Or higher. When the foam of the present invention is applied to a cold beam refrigerated vacuum insulation material, the thermal insulation effect is good, and its thermal conductivity can be reduced to 0.01 W / mk after being evacuated. Since the foam of the present invention does not contain a refrigerant, it does not damage the ozone layer. The main raw materials used in the PU foam of the present invention are polyether polyols and polyisocyanates, which are the raw materials used in general conventional rigid PU foams. The starting materials for the synthesis of the polyether polyols are mainly sucrose and glycerol. -5 functional groups and a value of 300 ~ 700 mgKOH / g; the polyisocyanate g is mainly a mixture of MDI and a highly functional isocyanate, and its functional group is about 2.7. The formation of small pores and polymer scaffolds is conducive to reducing heat conduction. On PU foam using refrigerant, there is only a simpler gelation reaction, and the foaming phenomenon is mainly a physical phenomenon of refrigerant evaporation and expansion. Since we only use water as the foaming agent, we must completely release the ^ _ oxide gas to cause swelling through the chemical reaction between water and isocyanate, that is, the foaming reaction and the gelation reaction are performed simultaneously. These two reactions require There is proper balance, and the use of catalysts has a critical impact on balance. The catalyst used in the formulation of the present invention mainly belongs to tertiary amine compounds, such as DMDEE, τ EDA, TD-33, and PMDETA, etc. In the present invention, the time from when the A liquid and the B liquid are mixed to the instant when foaming and expansion begin is The development time is taken as the reference value of the foaming rate, and the time after the reactants are mixed until the foam skin is not sticky is the "non-sticky time" as the reference value for the gelation rate. The experimental results show that the increase in the amount of catalyst caused When the gelation rate is increased, the formed polymer scaffolds have a smaller tendency (the first, second, and third tests, the fourth, fifth, and sixth tests, and the seventh and eighth tests respectively in Example 1 below). The test is a group of comparisons. ° The appropriate catalyst dosage is 0.2 to 3% (in terms of

564253

Polyether polyortho-alcohol is based on weight). Adding a diol-based chain extender hardly affects the reaction rate, but has a reducing effect on the polymer scaffold and the average pore diameter (see Example 2, comparing g ~ 1 ^ test with the second test as a group), The amount of chain extender is 0.2 ~ 2. (Based on the weight of polyether polyol), the most suitable chain extender is propylene glycol [Propylene glyC0i, (herein referred to as pEG)], B Diol — [Diethylene glycol, (herein referred to as DEG)]. On the other hand, water acts as a foaming agent and a cross-linking agent, and has an effect on the pore diameter and density of the foam x (Example 3). The amount of water used is from 0.2 to 2.5% (based on the weight of polyether polyol). _ Because the foam has an open-cell structure and does not have the support of closed-cell bubbles, it is easier to collapse and shrink. Adding an additional cross-linking agent can harden the foam. Because of its high activity, the dosage must be carefully considered to Avoid the formation of excessive breaking and branching points' The amount of additional crosslinking agent is 0.4 ~ 丨% (based on the weight of the polyether polyol). The most suitable crosslinking agent is diethanolamine [Diethan〇Umine,-(herein referred to as DIE)]. Due to the use of complete water foaming, the surfactant uses a non-hydrolyzable polysiloxane polymer. The amount of the surfactant has a great influence on the porosity and pore size. A proper surfactant can form a good pore size and porosity ( Example 4), the amount of the surfactant is 1 to 3.6% (based on the weight of the polyether multiple weight). The most suitable surfactant is the United States. Niax silicone L-6 1 6 4 . When the foam is formed into a relatively small pore size and a polymer stent, and has a good porosity, it can be packaged into a vacuum insulation sheet to reduce the heat conduction (Example 5).

564253 __Case No. 89105188 July / 〇 fz_ Amendment _ V. Description of the invention (6) Polyol weight is used as the basis. Example 1 100 parts by weight of a polyether polyol (number of functional groups: 4.3, hydroxyl value: 49 0), 2 parts by weight of water, 3 parts by weight of a surfactant [Niax si 1 icone L-6164 produced by Osi], and a catalyst After mixing evenly, material A is preheated at a temperature of 2 7 ° C ~ 33 ° C, and material B is a polyisocyanate (mainly a mixture of MDI and a highly functional isocyanate, and the number of functional groups is 2.7) to a temperature of 27 t. ~ 3 3 ° C for preheating '. After the temperature is uniform, put it into the bucket of the two-step foaming machine, mix the A and B materials through the foaming machine and inject the temperature to 37 ° C. (; Λ foamed in the mold of Λ. The type and amount of catalyst, and the Shaw reaction results of polyisocyanate are listed in the following table. Average pore diameter (mm) 0. 088 0. 092 0. 085 0.097 0.082 0.076 0.115 0. 103 Not sticky ^ Time 3 minutes 3 5 seconds 2 minutes 1 4 seconds 56 seconds 3 minutes 1 0 seconds 2 minutes 31 seconds 1 minute 47 seconds 8 minutes 2 5 seconds 2 minutes 1 3 seconds Polymer ° · 033 〇 03 0 · 027 0 · 026 0 · 025 0 · 021 ° · 036 0 · 026 Trial of isocyanate catalyst for acid coating purpose__ Time 1 122% 0.4 ° / 〇 (TEDA) 52 seconds 2 120% 0. 6% (TEDA) 37 seconds 3 122% 1% (TEDA) 23 seconds 4 9 6 ° / 〇0 · 8% (TD-33) 5 9 seconds 5 9 2 ° / 〇1 · 20 / 〇 (TD-33) 5 3 seconds 6 92% 1.6% (TD-33) 39 seconds 788% 0.2% (PMDETA) 35 seconds 8 88% 0.4% (PMDETA) 21 seconds

Page 10 564253 Case No. 89105188 In July, ο Amendment V. Description of the invention (7) Frame, and good openness (above 80%). In addition, when the amount of catalyst is increased, the gelation rate will be increased, and the polymer scaffolds formed will tend to decrease. Example 2 The procedure of Example 1 was repeated except that the catalyst was limited to 0.6 parts by weight of TEDA and a chain extender was further added. The type and amount of chain extender, the amount of polyisocyanate, and the reaction results are listed in the table below.

Test isocyanate chain extender average pore polymer scaffold _ (mm) (mm) 9 122% 0.4% (PEG) 0.08 0.023 10 122% 0.8% (PEG) 0.885 0.027 11 110% 1.2% (PEG) 0.07 0. 029 12 98% 1.8 ° / 〇 (PEG) 0.079 0.02 021 13 96% 0.4% (DEG) 0.072 0.019 14 102 % 1% (DEG) 0.079 0. 024 15 100% 1.8 ° / 〇 (DEG) 0.067 0.026 16 100% 2.4% (DEG) 0.075 0.021

It can be seen from the comparison between the second test of the example and the above table that the use of the chain extender has the effect of reducing the size of the cells and the polymer scaffold. Example 3 In addition to the chain extender defined as 1.2 parts by weight of DEG and the amount of changing water

Page 11 564253 Amendment No. 89105188 V. Description of the invention (8) Repeat the steps of the second embodiment. The amount of water, the amount of polyisocyanate and the reaction results are listed in the table below. Test isocyanate average pore size (mm) Polymer stent (mm) Density (kg / m3, 17 104% 0. 6% 0. 068 0.023 102 18 102% 1% 0. 081 0. 023 62 19 10% 2.2 2 % 0.067 0. 025 63 From the data in the table above, it can be seen that the amount of water has an effect on the pore size and density of the foam. The amount of water can form a finer when 0.6% (based on the weight of polyether polyol). Example 4 In addition to limiting water to 2 parts by weight, additional 0.6 parts by weight of cross-linking agent DIE and varying N ia X si 1 ic ο ne L _ 6 1 6 4 surfactant In addition to the amount used, the steps of Example 3 were repeated. The amount of Niax silicone L-6164 surfactant and the reaction results are listed in the table below.

Isocyanate interface average pore size polymer scaffold acetate active agent (mm) (ram) Porosity 20 92 ° / 〇1 ° / 〇0.095 0.019 95.4% 21 93% 1. 6 ° / 〇.0.0 0.016 89 8% 22 93% 2 ° / 〇0.087 0.018 94.5% Page 12 564253

Case No. 89105j @ V. Description of the invention (9) It can be seen from the information in the table above that non-k & 1.1 ffl ^ ^ 1% (^ ^ ^ ^ right-dissolving polysiloxane polymer surfactant is used in 1 Μ The finer the polyol is, the better the foam is A. The fine pore diameter can be formed when Example 5 uses 100 parts by weight of a polyether polyhydric, ΠΛ, 9 and more. 0 _ Xiwu functional group number 4 · 3, Hydroxyl value 490) 2 parts by weight of wound water V-. • r τ Surfactant [Niax silicone L-6164 produced by Si], 1.2 Weight price ladder μ ± η η β Non-trauma bond increasing agent DEG, 0.6 parts by weight of catalyst TEDA and 0.6 parts by weight of 1 crosslinking agent die, w. a 1 β and 8 9 parts by weight of polyisocyanate (mainly MDI and highly functional isocyanate & 2. "A hard PU open-cell foam was prepared according to the procedure of m: properties are listed below Table. From the data in the following table, it can be seen that the rigid PU open-cell foam of this example has a small pore size and a polymer stent, and has a good open cell ratio. When it is packaged with a thermal insulation sheet, it can reduce heat conduction. Purpose: Thermal conductivity of packaged vacuum sheet, W / mk 0. 01

The average polymer is not encapsulated into a test hole holder vacuum sheet heat transfer ^ LmL · LrnL · Opening car w / mk 230.068 0.019 95.7% 0 · 〇38 Comparative Example: 100 parts by weight of a polyether polyol (number of functional groups 4.5 , Hydroxyl value 36〇), polyisocyanate (mainly a mixture of MDI and a highly functional isocyanate, the number of functional groups 2 · 7) and the ingredients listed in the table below to prepare hard

Page 13 564253 Case number 89105188

Ling Nian? Month / Q Amendment V. Description of the invention (10) Quality PU foam test of isocyanate—24 1 2 4% 3% Catalyst # potassium acetate-1.5% calcium stearate-1.5% DMDEE 3%- 27 116% 1.4% potassium acetate 0.2% Y- 1 0 76 2 * + DMDEE 0.2% 8% 28 116% 1.4% potassium acetate 0.2% L-6164 + DMDEE 0.2% 1% OSi Silicon Y- 1 0 7 6 2 2 5 1 2 4% 3% 2 6 1 2 4% 3% Mean pore diameter of surfactant mm) # # 0. 155 0.160

氺 From the information in the table above, it can be seen that the results of improper catalyst composition or the ineffective formation of foam without the use of surfactants, or the formation of coarse foam pores and scaffolds.

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Claims (1)

564253 Announcement · ^ Qin No. 89105188 IH 6th, the scope of patent application 1 · A composition of a rigid polyurethane open-cell foam, comprising liquid A and liquid B, where liquid A contains: 100 Parts by weight of a polyether polyol having 3 to 5 hydroxyl functional groups and a hydroxyl value of 300 to 700 mgKOH / g; 1 to 3.6 parts by weight of a non-hydrolyzable polysiloxane surfactant; 0.2 to 3 parts by weight Tertiary amine catalyst; 0.2 to 2.6 parts by weight of water; and 0.2 to 2.4 parts by weight of carbon atoms C2-C8 polyol chain extender; and the B liquid contains a polyisocyanate, wherein the B liquid The weight ratio with α liquid is between 0.7 ~ 1.2. 2. The composition according to item 1 of the patent application range, wherein the liquid A further contains 0.4 to 1% by weight of a cross-linking agent selected from the group consisting of diethanolamine, glycerol, and triethanolamine composition. Wherein the parent crosslinker is 3. The composition as claimed in item 1 of the scope of patent application 4. The composition as claimed in item 1 of the scope of patent application, wherein the polyisocyanate is a polyisocyanate having a functional group of 2-3. 5. The composition according to item 4 of the patent application, wherein the polyisocyanate is selected from the group consisting of bisphenylphenylmethane diisocyanate (MDI), and tolyldimethycyanate (TDI) , Hexamethylene diisocyanate 'isophorone diisocyanate_' monotoluene diisocyanate, tribenzyl Page 16 564253 Amendment No. 89105188 6. Composition of patent application methane triisocyanate and mixtures thereof 6. The composition of item 5 of the patent application scope, wherein the polyisocyanate is an isocyanate functional group containing 2.7 containing MDI Isocyanate mixture. 7. The composition according to item 1 of the application, wherein the polyol chain extender is propylene glycol or ethylene glycol. 8. The composition according to item 1 in the scope of the patent application, wherein the tertiary amine catalyst is 2, 2'-dimorphine diethyl ether [2, 2'-dimorphine diethyl ether Dimorpholinodiethylether], Triethylenediamine, or Pentamethyldiethylenetriamine 〇9. The composition of item 1 in the scope of patent application, wherein the polyether polyol is selected from glycerol, sucrose or A polyether polyol prepared by polymerizing a polyfunctional alcohol of hexaol with an alkylene oxide. 10. A method for manufacturing a rigid polyurethane open-cell foam, comprising the following steps: a) mixing 100 parts by weight of 3 to 5 hydroxyl functional groups and a hydroxyl value of 300 to 70〇11 ^ 2 至 2. 6 重量 份 的 [011 / bogey polymysterol, 1 to 3.6 parts by weight of a non-hydrolyzable polysiloxane surfactant, 0.2 to 3 parts by weight of a tertiary amine catalyst, 0.2 to 2.6 parts by weight Water, and C2 to C8 polyols having 0.2 to 2.4 parts by weight of carbon atoms Page 17 564253 Amendment No. 89105188 6. Applying a patent for a chain extender to prepare a liquid A; b) preheating the liquid A in step a) to keep it at a temperature of 2 5 -45 ° C; c) Hot polyisocyanate B liquid is kept at a temperature of 2 5-45 ° C; d) Preheated liquid A and liquid B are rapidly added at a ratio of liquid B to liquid A weight of 0.7 ~ 1.2 Pre-mixing, and then the obtained mixture is injected into a mold at a temperature of 3 5 -5 5 ° C and a temperature higher than the mixture of liquids A and B is simultaneously cured and foamed; and e) from the mold An open-cell polyurethane foam was removed inside. 11. The method of claim 10, wherein the curing and foaming time of the mixture of liquid A and liquid B in the mold in step d) is 2 minutes to 10 minutes. Page 18