CN103087288B - Low-VOC (volatile organic compound) high-resilience polyurethane foam and preparation method thereof - Google Patents
Low-VOC (volatile organic compound) high-resilience polyurethane foam and preparation method thereof Download PDFInfo
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Abstract
The invention provides a low-VOC (volatile organic compound) high-resilience polyurethane foam and a preparation method thereof. The low-VOC high-resilience polyurethane foam is prepared from polyether glycol mixture and isocyanate mixture in a weight ratio of (100:43)-(100:58), wherein the polyether glycol mixture is prepared from the following raw materials in parts by weight: 60 parts of polyether glycol, 40 parts of polymer polyalcohol, 3.0-3.8 parts of water, 0.7-0.9 part of catalyst, 0.8-2.0 part of crosslinking agent and 0.55-0.75 part of silicon oil. The technical scheme provided by the invention greatly enhances the comfort and durability of the polyurethane foam product, obviously reduces the cost, and comprehensively lowers the toxic and harmful substances in the product.
Description
Technical field
The invention belongs to polyurethane foam and manufacture field, especially relate to a kind of low VOC high resilience polyurethane foam and preparation method thereof.
Background technology
Comfortableness is automotive field important topic, after passenger enters automobile, the first contiguous sense from automotive seat, good comfort property improving product intangible value.Automotive seat soft comfortable main carriers is polyurethane foam.Various countries slip-stick artist is devoted in making foam field the optimal foaming proportioning raw materials studying intensively safety, comfort aspect always.
Patent 200810225474.0 discloses a kind of all-MDI polyurethane height rebound foam, and prepared by following raw material: A.MDI system isocyanate, functionality is 2.1 ~ 2.5; B. polyether polyatomic alcohol component; C. whipping agent; D. catalyzer; E. tensio-active agent; Patent 200610070711.1, discloses a kind of preparation method of all-MDI polyurethane height rebound foam.Above-mentioned polyurethane high resilience foam is and adopts MDI system to produce, MDI system is partially hard, the various performance index of this system foam process are up to state standards all reluctantly, and it is high to there is production cost, foam hardness is large, and comfort level is poor, and product durability degree is not high, the problems such as VOC content is high, so the slip-stick artist of increasing producer and various countries endeavours to study when technological process of filling a prescription on the basis of M/T system.
Summary of the invention
The problem to be solved in the present invention is to provide low VOC high resilience polyurethane foam of a kind of M/T system and preparation method thereof, is especially suitable in automotive seat.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of low VOC content high resilience polyurethane foam, and raw material comprises polyether glycol compound and isocyanic ester compound; Wherein, polyether glycol compound: the weight ratio of isocyanic ester compound is (100:43)-(100:58).Join the different hardness of specific internal energy adjustment foam at this, the requirement of client to seat each position different hardness can be met, adapt to body mechanics, better improve seat comfort.As: automotive seat front stall foam middle part polyether glycol compound: the weight ratio of isocyanic ester compound is 100: 45, and both sides are 100: 58; Front by foam middle part polyether glycol compound: the weight ratio of isocyanic ester compound is 100: 43, and both sides are 100: 54.
Polyether glycol compound comprises polyether glycol, polymer polyatomic alcohol, whipping agent, catalyzer, linking agent and silicone oil.
Polyether glycol compound Raw weight ratio is:
Polyether glycol: 60 parts
Polymer polyatomic alcohol: 40 parts
Water (as whipping agent): 3.0-3.8 part
Catalyzer: 0.7-0.9 part
Linking agent: 0.8-2.0 part
Silicone oil: 0.55-0.75 part;
Described isocyanic ester compound is the isocyanic ester of BASF AG CW5010-102C-B model.
Described catalyzer is NE1070 type and the NE300 type catalyzer of aerification chemical product company limited of the U.S. or is selected from U.S.'s Hensel DPA type advanced in years and LED103 type catalyzer.In said ratio, this catalyzer is the model of current cost and VOC content cost performance optimum, and catalysis can improve foam hard and tensile strength gross weight.Preferably, NE1070 type: the weight ratio of NE300 type catalyzer is 4: 1; DPA type: the weight ratio of the catalyzer of LED103 type is 3:1.
Described silicone oil is DC2525 type and the DC6070 type silicone oil of aerification chemical product company limited of the U.S., in said ratio, can improve foam cell structure and stable foam is capillary, and reduces the VOC content of finished product further.Preferably, DC2525 type: the weight ratio of DC6070 type is 5: 1.
Preferably, described polyether glycol is can the KE810 type polyether glycol of Leah polyvalent alcohol (Nanjing) company limited; Described polymer polyatomic alcohol is can the FA3630S type polymer polyatomic alcohol of Leah polyvalent alcohol (Nanjing) company limited.Described KE810 type polyether glycol is that relative molecular weight can remain on 5000-6500, the ethylene oxide-capped polyether triol high activity polyether of hydroxyl value 28mgKOH/g.Described FA3630S type polymer polyatomic alcohol is a kind of organic filler polyvalent alcohol, can replace mineral filler, KE810 and FA3630S type with the use of, polyurethane foam supporting capacity, rebound resilience, foam structure, physical and mechanical properties maximum amplitude can be made to improve.
Described linking agent is BASF AG DEOA diethanolamine and TEOA trolamine, wherein the weight ratio of DEOA diethanolamine and TEOA trolamine is 3: 5, described linking agent is containing multi-functional active dydrogen compounds, it is the distinctive Synergist S-421 95 of high rebound foam, in said ratio, there is good effect to the hardness and resilience improving foam.
Above-mentioned raw materials all can commercially availablely obtain.
Present invention also offers a kind of method of described low VOC content high resilience polyurethane foam, comprise the steps:
1, using the polyether glycol compound after isocyanic ester compound and pre-mixing as raw material respectively stored in storage tank; Preferably, the temperature being stored in storage tank Raw is 20 DEG C-26 DEG C, and raw material rises sends out velocity balance, and foam-formed property is stablized.
2, by raw material by storage tank by high-pressure pump, be evenly cast in the die cavity that is made up of upper die and lower die, the temperature of upper die and lower die controls at 60 DEG C ± 5 DEG C, and foam-formed slaking is good, and macroscopic irregularity is few, not decortication and Burn defect.Preferably, the outer wall of upper die and lower die is respectively equipped with the water pipe be connected with die heater, the temperature of die heater passes to upper and lower mould by water pipe, carries out heat trnasfer by water pipe to upper and lower mould.
3, matched moulds reaction post curing is shaping.Preferably, the matched moulds reaction times is 3-4 minute.
The cost of polyurethane foam is by core density (Kg/m
3) determine, density height then cost is high; Product durability degree is determined by elongation at break (%), tensile strength (KPa), comfortableness is determined by 40% indentation force deflection (N), falling-rebounding ball rate (%), only has 40% indentation force deflection in standard value range, and falling-rebounding ball rate is greater than 60%, seat comfort just can be higher.Contriver is through lot of experiments, mainly through the proportioning between the selection, each raw material of the concrete model to polyurethane foam raw material, and polyether glycol compound, isocyanic ester compound weight ratio start with, prepare polyurethane foam finished product comfortableness, durability of product all has and promote by a relatively large margin, and cost obviously lowers, and the product venomous injurant obtained reduces comprehensively.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but do not limit protection scope of the present invention.
Raw material information involved in embodiment is as follows:
Polyether glycol 810: can the KE810 type polyether glycol of Leah polyvalent alcohol (Nanjing) company limited
Polyether glycol 330: the polyether glycol EP330N of Shandong blue star Dong great Chemical Co., Ltd.
Polyether glycol 1618: the polyether glycol 1618 of Historic Area of Zhongshan in Nanjing City Chemical Co., Ltd.
Polymer polyatomic alcohol 36/30: can the FA3630S type polymer polyatomic alcohol of Leah polyvalent alcohol (Nanjing) company limited
Polymer polyatomic alcohol 36/28: the polymer polyatomic alcohol POP36/28 of Shandong blue star Dong great Chemical Co., Ltd.
Polymer polyatomic alcohol 104: the polymer polyatomic alcohol 104 of Historic Area of Zhongshan in Nanjing City Chemical Co., Ltd.;
Catalyzer DPA: the DPA type catalyzer that U.S.'s Hensel steps.
Catalyzer LED103: the LED103 type catalyzer that U.S.'s Hensel steps.
Linking agent: BASF AG DEOA diethanolamine and TEOA trolamine, wherein the weight ratio of DEOA diethanolamine and TEOA trolamine is 3: 5.
Isocyanic ester CW5010 C-B: the isocyanic ester of the CW5010-102 C-B model of BASF AG.
Isocyanic ester CW-5045: the isocyanic ester of the CW-5045 model of BASF AG.
Silicone oil is DC2525 type and the DC6070 type silicone oil of aerification chemical product company limited of the U.S..
In embodiment, the preparation method of polyurethane foam is as follows:
(1) by the proportioning of filling a prescription described in embodiment, by the polyether glycol compound (obtaining after polyether glycol, polymer polyatomic alcohol, water, catalyzer, linking agent and silicon pre-mixing by ordinary method) after isocyanic ester and pre-mixing as raw material respectively stored in storage tank, the temperature controlling storage tank Raw is 20 DEG C-26 DEG C;
(2) by raw material by storage tank by high-pressure pump, be evenly cast in the die cavity that is made up of upper die and lower die, the temperature of upper die and lower die controls at 60 DEG C ± 5 DEG C.The outer wall of upper die and lower die is respectively equipped with the water pipe be connected with die heater, and the temperature of die heater passes to upper and lower mould by water pipe, carries out heat trnasfer by water pipe to upper and lower mould.
(3) matched moulds reaction post curing is shaping, and the matched moulds reaction times is 3-4 minute;
(4) delivery, post curing, obtains polyurethane foam.
Embodiment 1
Table 1
| Sequence number | 1-1 | 1-2 | 1-3 | 1-4 | 1-5 |
| Formula | Weight (g) | Weight (g) | Weight (g) | Weight (g) | Weight (g) |
| Polyether glycol 810 | 60 | 60 | |||
| Polyether glycol 330 | 60 | 60 | |||
| Polyether glycol 1618 | 60 | ||||
| Polymer polyatomic alcohol 36/30 | 40 | ||||
| Polymer polyatomic alcohol 36/28 | 40 | 40 | |||
| Polymer polyatomic alcohol 104 | 40 | 40 | |||
| Catalyst A-33 | 0.49 | 0.49 | 0.49 | 0.49 | 0.49 |
| Catalyst A-1 | 0.16 | 0.16 | 0.16 | 0.16 | 0.16 |
| Whipping agent (water) | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 |
| Silicone oil Y-10366 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 |
| Linking agent | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 |
| Isocyanic ester CW-5045 | 100∶45 | 100∶45 | 100∶45 | 100∶45 | 100∶45 |
| Isocyanate index | 100 | 100 | 100 | 100 | 100 |
| VOC content | 44.31 | 46.85 | 67.36 | 53.62 | 59.85 |
| Elongation at break (%) | 89.3 | 82.5 | 90.3 | 91.6 | 93.8 |
| Tensile strength (KPa) | 152.4 | 168.5 | 152.8 | 163.9 | 143.2 |
| Tear strength (N/cm) | 1.85 | 1.93 | 2 | 2.12 | 1.96 |
| Falling-rebounding ball rate (%) | 56.9 | 54.5 | 55.8 | 53.3 | 55.9 |
| Core density (Kg/m 3) | 59.88 | 60.32 | 61.25 | 61.03 | 60.53 |
| 75% compression set (%) | 8％ | 7％ | 7％ | 8％ | 6％ |
| 40% indentation force deflection (N) | 104.5 | 109.6 | 102.3 | 98.6 | 103.1 |
As can be seen from Table 1, the polyurethane foam VOC content that the polyurethane material used at present is produced is higher, all more than 40ppm. wherein 1-3 reach 67.3ppm.Compare with embodiment 4 with embodiment 3, product foam property in table 1 is all poor, density, hardness are high, resilience is low, illustrate that foam comfortableness is bad, but under above formula same case, the polyethers 810+ polymkeric substance 36/30 combination foam VOC content of 1-1 is relatively low, density, hardness are high, and resilience is relatively better.
Embodiment 2
Table 2
| Sequence number | 2-1 | 2-2 | 2-3 | 2-4 | 2-5 |
| Formula | Weight (g) | Weight (g) | Weight (g) | Weight (g) | Weight (g) |
| Polyether glycol 810 | 60 | 60 |
| Polyether glycol 330 | 60 | 60 | |||
| Polyether glycol 1618 | 60 | ||||
| Polymer polyatomic alcohol 36/30 | 40 | ||||
| Polymer polyatomic alcohol 36/28 | 40 | 40 | |||
| Polymer polyatomic alcohol 104 | 40 | 40 | |||
| Catalyst A-33 | 0.49 | 0.49 | 0.49 | 0.49 | 0.49 |
| Catalyst A-1 | 0.16 | 0.16 | 0.16 | 0.16 | 0.16 |
| Whipping agent (water) | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 |
| Silicone oil B8681 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 |
| Linking agent | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 |
| Isocyanic ester CW5045 | 100∶45 | 100∶45 | 100∶45 | 100∶45 | 100∶45 |
| Isocyanate index | 100 | 100 | 100 | 100 | 100 |
| VOC content | 40.77 | 42.33 | 53.24 | 48.67 | 51.23 |
| Elongation at break (%) | 82.5 | 86.91 | 88.02 | 90.13 | 85.72 |
| Tensile strength (KPa) | 168.5 | 152.6 | 157.3 | 152.7 | 163.2 |
| Tear strength (N/cm) | 2 | 1.9 | 1.87 | 1.89 | 1.97 |
| Falling-rebounding ball rate (%) | 53.8 | 55.1 | 54.3 | 56.5 | 57.2 |
| Core density (Kg/m 3) | 60.04 | 59.81 | 60.33 | 60.75 | 61.06 |
| 75% compression set (%) | 7％ | 8％ | 8％ | 6％ | 7％ |
| 40% indentation force deflection (N) | 103.05 | 106.84 | 107.32 | 114.56 | 107.68 |
As can be seen from Table 2: change after silicone oil, the polyurethane foam VOC content obtained is still higher, all low than the finished product of the table 1 in embodiment 1 more than 40ppm..Compare with 4 with embodiment 3, the foam property in table 2 is all poor, and density, hardness are high, resilience is low, and foam comfortableness or bad is described, but under formula same case, polyethers 810+ polymkeric substance 36/30 combination foam VOC content is relatively low, and density, hardness are high, and resilience is relatively better.
Embodiment 3
Table 3
| Sequence number | 3-1 | 3-2 | 3-3 | 3-4 | 3-5 |
| Formula | Weight (g) | Weight (g) | Weight (g) | Weight (g) | Weight (g) |
| Polyether glycol 810 | 60 | 60 | |||
| Polyether glycol 330 | 60 | 60 | |||
| Polyether glycol 1618 | 60 | ||||
| Polymer polyatomic alcohol 36/30 | 40 | ||||
| Polymer polyatomic alcohol 36/28 | 40 | 40 | |||
| Polymer polyatomic alcohol 104 | 40 | 40 | |||
| Catalyst n E1070 | 0.60 | 0.60 | 0.60 | 0.60 | 0.60 |
| Catalyst n E300 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 |
| Whipping agent (water) | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 |
| Silicone oil DC2525 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Silicone oil DC6070 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Linking agent | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 |
| Isocyanic ester CW5010C-B | 100∶47 | 100∶47 | 100∶47 | 100∶47 | 100∶47 |
| Isocyanate index | 101 | 101 | 101 | 101 | 101 |
| VOC content | 24.01 | 27.31 | 34.85 | 30.02 | 32.46 | |
| Elongation at break (%) | 107 | 102 | 104 | 101 | 106 | |
| Tensile strength (KPa) | 244 | 210 | 215 | 226 | 238 | |
| Tear strength (N/cm) | 2.4 | 2.2 | 2.34 | 2.21 | 2.18 | |
| Falling-rebounding ball rate (%) | 62.2 | 61.5 | 63.1 | 62.8 | 60.3 | |
| Core density (Kg/m 3) | 54.8 | 55.3 | 55.1 | 55.8 | 56.2 | |
| 75% compression set (%) | 8％ | 8％ | 7％ | 8％ | 8％ | |
| 40% indentation force deflection (N) | 76 | 75.3 | 74 | 72.6 | 74.5 |
As can be seen from Table 3: when the catalyzer in formula is catalyst n E1070 and catalyst n E300, and both ratios are 4: 1, silicone oil is silicone oil DC2525 and DC6070, and DC2525:DC60705:1, when isocyanic ester is the isocyanic ester of CW5010CB model, the polyurethane foam VOC content obtained obviously reduces, lower than 25ppm, and foam property all significantly improves, density, hardness reduces, resilience improves, illustrate that foam comfortableness significantly improves, can see simultaneously, the polyethers 810+ polymkeric substance 36/30 combination foam VOC content of 3-1 is relatively low, density, hardness is high, resilience is relatively better.
Embodiment 4
Table 4
| Sequence number | 4-1 | 4-2 | 4-3 | 4-4 | 4-5 |
| Formula | Weight (g) | Weight (g) | Weight (g) | Weight (g) | Weight (g) |
| Polyether glycol 810 | 60 | 60 | |||
| Polyether glycol 330 | 60 | 60 | |||
| Polyether glycol 1618 | 60 | ||||
| Polymer polyatomic alcohol 36/30 | 40 | ||||
| Polymer polyatomic alcohol 36/28 | 40 | 40 | |||
| Polymer polyatomic alcohol 104 | 40 | 40 | |||
| Catalyzer DPA | 0.69 | 0.49 | 0.49 | 0.49 | 0.49 |
| Catalyzer LED103 | 0.23 | 0.16 | 0.16 | 0.16 | 0.16 |
| Whipping agent (water) | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 |
| Silicone oil DC2525 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Silicone oil DC6070 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Linking agent | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 |
| Isocyanic ester CW5010C-B | 100∶47 | 100∶47 | 100∶47 | 100∶47 | 100∶47 |
| Isocyanate index | 101 | 101 | 101 | 101 | 101 |
| VOC content | 23.76 | 28.01 | 33.12 | 31.28 | 32.19 |
| Elongation at break (%) | 108 | 107 | 107 | 107 | 107 |
| Tensile strength (KPa) | 236 | 203 | 218 | 221 | 215 |
| Tear strength (N/cm) | 2.38 | 2.12 | 2.15 | 2.19 | 2.23 |
| Falling-rebounding ball rate (%) | 63.7 | 62.2 | 61.5 | 62.7 | 61.8 |
| Core density (Kg/m 3) | 53.9 | 54.8 | 55.4 | 54.2 | 55.9 |
| 75% compression set (%) | 7％ | 8％ | 8％ | 7％ | 7％ |
| 40% indentation force deflection (N) | 74.6 | 75.9 | 73.1 | 73 | 74.7 |
As can be seen from Table 4: compared with embodiment 3, other are constant only to use catalyzer instead, the polyurethane foam VOC content of production is substantially identical, also lower than 25ppm.And foam property is substantially identical with example 3, density, hardness are lower, and resilience is greater than 60%, illustrate that foam comfortableness is better, and catalyst n E1070+NE300 and DPA+LED103 produces foam and meet design requirements to VOC content and foam property.In addition, can see that, under other raw material same cases of formula, from the over-all properties of product, especially VOC content, density, hardness, resilience aspect, the polyethers 810+ polymkeric substance 36/30 of 4-1 combines the foam finished product obtained and is obviously better than other a few group of formula.
The product that the product (M/T namely in table) and the traditional MDI system that obtain with 3-1 in embodiments of the invention 3 prepare compares, and result as shown in table 5 and table 6.Can see from table 5 and table 6, owing to have employed technical scheme of the present invention, the comfortableness of polyurethane foam, durability of product all have and promote by a relatively large margin, and cost obviously lowers, and the product venomous injurant obtained reduces comprehensively.
Table 5
Table 6
Above preferred embodiment of the present invention has been described in detail, but described content being only preferred embodiment of the present invention, can not being considered to for limiting practical range of the present invention.All equalizations done according to the present patent application scope change and improve, and all should still belong within patent covering scope of the present invention.
Claims (9)
1. a low VOC high resilience polyurethane foam, is characterized in that: raw material comprises polyether glycol compound and isocyanic ester compound; Wherein, polyether glycol compound: the weight ratio of isocyanic ester compound is (100:43)-(100:58);
Described polyether glycol compound is made up of the raw material comprising following parts by weight:
Described isocyanic ester compound is the isocyanic ester of BASF AG CW5010-102 C-B model;
Described catalyzer is NE1070 type and the NE300 type catalyzer of aerification chemical product company limited of the U.S. or is selected from U.S.'s Hensel DPA type advanced in years and LED103 type catalyzer.
Described silicone oil is DC2525 type and the DC6070 type silicone oil of aerification chemical product company limited of the U.S..
2. low VOC high resilience polyurethane foam according to claim 1, is characterized in that: NE1070 type: the weight ratio of NE300 type catalyzer is 4:1; DPA type: the weight ratio of the catalyzer of LED103 type is 3:1.
3. low VOC high resilience polyurethane foam according to claim 1 and 2, is characterized in that: DC2525 type: the weight ratio of DC6070 type silicone oil is 5:1.
4. low VOC high resilience polyurethane foam according to claim 3, is characterized in that: described polyether glycol is can the KE810 type polyether glycol of Leah polyvalent alcohol (Nanjing) company limited; Described polymer polyatomic alcohol is can the FA3630S type polymer polyatomic alcohol of Leah polyvalent alcohol (Nanjing) company limited.
5. low VOC high resilience polyurethane foam according to claim 4, is characterized in that: described linking agent is BASF AG DEOA diethanolamine and TEOA trolamine, and wherein the weight ratio of DEOA diethanolamine and TEOA trolamine is 3:5.
6. prepare a method for the low VOC high resilience polyurethane foam described in any one of claim 1-5, it is characterized in that: comprise the steps:
(1) using the polyether glycol compound after isocyanic ester compound and pre-mixing as raw material respectively stored in storage tank;
(2) by raw material by storage tank by high-pressure pump, be evenly cast in the die cavity that is made up of upper die and lower die, the temperature of upper die and lower die controls at 60 DEG C ± 5 DEG C;
(3) matched moulds reaction post curing is shaping.
7. method according to claim 6, is characterized in that: in step (3), and the matched moulds reaction times is 3-4 minute.
8. the method according to claim 6 or 7, is characterized in that: on the outer wall of upper die and lower die, be respectively equipped with the water pipe be connected with die heater, and the temperature of die heater passes to upper and lower mould by water pipe.
9. the method according to claim 6 or 7, is characterized in that: the temperature being stored in storage tank Raw is 20 DEG C-26 DEG C.
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