CN111748070A - Low-aldehyde content slow-rebound polyurethane foam and preparation method thereof - Google Patents

Abstract

The invention discloses low-aldehyde content slow-rebound polyurethane foam and a preparation method thereof, belonging to the technical field of polyurethane foam. The purpose of the present invention is to reduce the content of aldehydes in polyurethane foam. The polyurethane foam of the present invention is prepared from polyether polyol, diethanolamine, deionized water, triethylenediamine, cell opener, lactic acid, glycerol, foam stabilizer, isocyanate and aldehyde removal agent. The method of the present invention is as follows: diethanolamine, triethylenediamine, foam stabilizer, cell opener, glycerol, 86% lactic acid and deionized water are sequentially added to the polyether polyol, and after stirring evenly, place in a mold Then, add L-lysine in turn, then add isocyanate, mechanically stir for 20s to 27s at 60 to 670 r/min, and wait for it to foam and mature. The aldehyde removing agent used in the invention is cheap and easy to obtain, has good aldehyde removing effect, low odor, low aldehyde content in the product and moderate resilience.

Description

Low-aldehyde content slow-rebound polyurethane foam and preparation method thereof

technical field

The invention belongs to the technical field of polyurethane foam, and in particular relates to the preparation of a low-aldehyde content slow-rebound polyurethane foam.

Background technique

Damping and shock absorption material is a material that can absorb the energy brought by vibration through its own movement and contraction, convert the mechanical energy given to the material itself by the outside world, convert it into heat energy and then emit the material itself. Polyurethane has a special soft segment-hard segment. Segment block structure, which lays the foundation for its use as a damping and vibration damping material. Polyurethane material has good sound insulation, shock absorption and energy absorption, and can be used to reduce vibration and noise caused by engines. It also has good oil resistance, excellent tensile strength and elongation at break, making it widely used in car seats. chairs and interiors, but the current polyurethane foam on the market has poor damping performance, and aldehydes are introduced into the raw materials for preparing polyurethane, which is a colorless gas with a strong irritating odor, mainly entering through the respiratory tract. The human body can also enter the human body through the skin, which is very harmful to the human body.

SUMMARY OF THE INVENTION

The purpose of the present invention is to reduce the content of aldehydes in the polyurethane foam; and to provide a low-aldehyde content slow-rebound polyurethane foam and a preparation method thereof.

In order to solve the above-mentioned technical problems, the low-aldehyde content slow-rebound polyurethane foam in the present invention is made from the following raw materials: polyether polyol 300N, diethanolamine, deionized water, triethylenediamine, pore opener, lactic acid, Glycerol, foam stabilizers, isocyanates and aldehyde scavengers.

Wherein, the aldehyde scavenger is one of L-lysine, solid amine, adipic acid dihydrazide, and nitrile acetamide, or a combination of several thereof.

Further limited, the parts by weight of each raw material are: 300N 55-60 parts of polyether polyol, 0.4-0.75 parts of diethanolamine, 3-4.5 parts of deionized water, 0.5-0.8 parts of triethylenediamine, 1 part of pore-opening agent -3 parts, 0.03-0.045 parts of lactic acid, 0.3-0.6 parts of glycerol, 0.4-0.65 parts of foam stabilizer, isocyanate, 32-38 parts; wherein, the parts by weight of each aldehyde removal agent are: L-lysine 1-4.2 parts, solid amine 1.5-2.6 parts, adipic acid dihydrazide 1.3-4.2 parts, nitrile acetamide 1.2-2.4, the dosage of the above-mentioned aldehyde scavenger is the same weight unit as other raw materials.

To be further limited, the mass ratio of the polyether polyol 300N to the isocyanate is (4.5-6):(2.4-3.8).

Further limited, the foam stabilizer is silicone oil B8002, silicone oil B8715 or silicone oil L626.

To be further limited, the pore-opening agent is pore-opening agent Y1900, pore-opening agent GK-350D or pore-opening agent GLK-15.

Further limited, the mass concentration of the lactic acid is 85% to 90%

It is further limited that the aldehyde scavenger is the compound of L-lysine and adipic acid dihydrazide; the weight ratio of L-lysine and adipic acid dihydrazide is (1～1.4):(3～ 4.2).

It is further limited that the aldehyde remover is the compound of L-lysine, solid amine and adipic acid dihydrazide; the weight ratio of L-lysine, adipic acid dihydrazide and solid amine is (1 ~ 1.2): (3～.36): (2～2.4).

It is further limited that the aldehyde removal agent is a compound of adipic acid dihydrazide and nitrile acetamide, and the weight ratio of adipic acid dihydrazide to nitrile acetamide is (1.3～1.5):(1.5～2.25 ).

The preparation method of the above-mentioned low-aldehyde content slow-rebound polyurethane foam is characterized in that the preparation method is carried out according to the following steps: adding diethanolamine, triethylenediamine, foam stabilizer, Cell opener, glycerol, lactic acid and deionized water, after stirring evenly, put them in the mold, then add aldehyde remover, then add isocyanate, mechanically stir at 600r/min～670r/min for 20s～27s, wait for It can be foamed and matured.

The aldehyde-removing agent adopted in the invention is cheap and easy to obtain, has good aldehyde-removing effect and has little odor.

The polyurethane foam of the invention has low aldehyde content and moderate resilience.

Detailed ways

Example 1: In parts by weight, the low-aldehyde content slow-rebound polyurethane foam in this implementation is made from the following raw materials: 58 parts of polyether polyol 300N, 0.54 parts of diethanolamine, 3.8 parts of deionized water, triethylene glycol 0.56 parts of base diamine, 2.2 parts of pore opener Y1900, 0.035 parts of lactic acid with a mass concentration of 86%, 0.5 parts of glycerol, 20.45 parts of foam stabilizer silicone oil B800, 1.2 parts of isocyanate, L-lysine, solid 1.7 parts of amine, 1.4 parts of adipic acid dihydrazide and 1.2 parts of nitrile acetamide; wherein, the mass ratio of the polyether polyol 300N to isocyanate is 5:3.

The preparation method of the above-mentioned low-aldehyde content slow-rebound polyurethane foam is carried out according to the following steps: successively adding diethanolamine, triethylenediamine, foam stabilizer silicone oil B8002, cell opener Y1900, propylene glycol to polyether polyol 300N Triol, lactic acid and deionized water, after stirring evenly, put them in the mold, then add L-lysine, adipic acid dihydrazide, solid amine and nitrile acetamide in sequence, and then add isocyanate, at 600r/min Next, use an electric stirrer to mechanically stir for 20s, and wait for it to foam and mature.

The lactic acid described in this implementation is a commercially available commodity, purchased from Tianjin Kemeiou Chemical Reagent Development Center.

Example 2: In parts by weight, the low-aldehyde content slow-rebound polyurethane foam in this implementation is made from the following raw materials: 56 parts of polyether polyol 300N, 0.6 parts of diethanolamine, 4 parts of deionized water, triethylene 0.58 part of base diamine, 152.5 part of pore opener GLK-152.5 part, 0.038 part of lactic acid with a mass concentration of 86%, 0.55 part of glycerol, 0.48 part of foam stabilizer silicone oil B87150, 36 part of isocyanate, 1.5 part of L-lysine , 1.85 parts of solid amine, 1.6 parts of adipic acid dihydrazide and nitrile acetamide: 1.4 parts; wherein, the mass ratio of the polyether polyol to isocyanate is 4.6:2.6.

The preparation method of the above-mentioned low-aldehyde content slow-rebound polyurethane foam is carried out according to the following steps: successively adding diethanolamine, triethylenediamine, foam stabilizer silicone oil B8715, and cell opener GLK-15 to the polyether polyol 300N , glycerol, lactic acid and deionized water, after stirring evenly, put them in the mold, then add L-lysine, adipic acid dihydrazide, solid amine, nitrile acetamide in turn, then add isocyanate, at 600r Use an electric stirrer to mechanically stir for 20s at /min, and wait for it to foam and mature.

Example 3: In parts by weight, the low-aldehyde content slow-rebound polyurethane foam in this implementation is made from the following raw materials: 56 parts of polyether polyol 300N, 0.54 parts of diethanolamine, 3.8 parts of deionized water, triethylene glycol 0.56 parts of base diamine, 2.2 parts of pore opener GK-350D, 0.035 parts of lactic acid with a mass concentration of 86%, 0.5 parts of glycerol, 0.45 parts of foam stabilizer silicone oil L6260, 1.2 parts of isocyanate and L-lysine; Wherein, the mass ratio of the polyether polyol to the isocyanate is 4.8:2.9.

The preparation method of the above-mentioned low-aldehyde content slow-rebound polyurethane foam is carried out according to the following steps: successively add diethanolamine, triethylenediamine, foam stabilizer silicone oil L626, and cell opener GK-350D to the polyether polyol 300N , glycerol, lactic acid and deionized water, after stirring evenly, put them in the mold, then add L-lysine in turn, then add isocyanate, mechanically stir with an electric stirrer for 20s at 600r/min, and wait for it to foam It can be matured.

Example 4: In parts by weight, the low-aldehyde content slow-rebound polyurethane foam in this implementation is made from the following raw materials: 58 parts of polyether polyol 300N, 0.60 part of diethanolamine, 4 parts of deionized water, triethylene 0.58 parts of base diamine, 152.5 parts of pore opener GLK-152.5 parts, 0.038 parts of lactic acid with a mass concentration of 86%, 0.55 parts of glycerol, 20.48 parts of foam stabilizer silicone oil B800, 1.6 parts of isocyanate and adipic acid dihydrazide, of which The mass ratio of the polyether polyol 300N to the isocyanate is 5.3:3.1.

The preparation method of the above-mentioned low-aldehyde content slow-rebound polyurethane foam is carried out according to the following steps: successively adding diethanolamine, triethylenediamine, foam stabilizer silicone oil B8002, and cell opener GLK-15 to the polyether polyol 300N , glycerol, lactic acid and deionized water, after stirring evenly, put them in the mold, then add adipic acid dihydrazide in turn, then add isocyanate, mechanically stir with an electric stirrer at 650r/min for 20s, wait for it to develop It can be soaked.

Example 5: In parts by weight, the low-aldehyde content slow-rebound polyurethane foam in this implementation is made from the following raw materials: 56 parts of polyether polyol 300N, 0.6 parts of diethanolamine, 4 parts of deionized water, triethylene 0.58 part of base diamine, 2.5 part of pore opener Y19000, 0.038 part of lactic acid with a mass concentration of 86%, 0.55 part of glycerol, 0.48 part of foam stabilizer silicone oil B87150, 1.85 part of isocyanate and solid amine; The mass ratio of polyether polyol to isocyanate is 5.5:3.4.

The preparation method of the above-mentioned low-aldehyde content slow-rebound polyurethane foam is carried out according to the following steps: successively adding diethanolamine, triethylenediamine, foam stabilizer silicone oil B8715, cell opener Y1900, propylene glycol to the polyether polyol 300N Triol, lactic acid and deionized water, after stirring evenly, put them in the mold, then add solid amine in turn, then add isocyanate, mechanically stir with an electric stirrer at 650 r/min for 23s, and wait for it to foam and mature.

Example 6: In parts by weight, the low-aldehyde content slow-rebound polyurethane foam in this implementation is made from the following raw materials: 56 parts of polyether polyol 300N, 0.6 parts of diethanolamine, 4 parts of deionized water, triethylene 0.58 part of base diamine, 0.58 part of pore opener GLK-152.5 part, 0.038 part of lactic acid with a mass concentration of 86%, 0.55 part of glycerin, 0.48 part of foam stabilizer silicone oil L6260, 0.45 part of isocyanate, L-lysine and hexanediol 1.35 parts of acid dihydrazide; wherein, the mass ratio of the polyether polyol to isocyanate is 5.6:3.6.

The preparation method of the above-mentioned low-aldehyde content slow-rebound polyurethane foam is carried out according to the following steps: successively adding diethanolamine, triethylenediamine, foam stabilizer silicone oil L626, and cell opener GLK-15 to the polyether polyol 300N , glycerol, lactic acid and deionized water, after stirring evenly, put them in the mold, then add L-lysine, adipic acid dihydrazide in turn, then add isocyanate, and use an electric stirrer at 670r/min. Stir for 25s, until it foams and matures.

Example 7: In parts by weight, the low-aldehyde content slow-rebound polyurethane foam in this implementation is made from the following raw materials: 60 parts of polyether polyol 300N, 0.8 parts of diethanolamine, 4 parts of deionized water, triethylene 0.58 part of base diamine, 2.5 part of pore opener GK-350D, 0.038 part of lactic acid with a mass concentration of 86%, 0.55 part of glycerol, 0.48 part of foam stabilizer silicone oil L6260, 0.45 part of isocyanate, L-lysine, 1.35 parts of adipic acid dihydrazide and 0.9 part of nitrile acetamide, wherein the mass ratio of the polyether polyol 300N to isocyanate is 5.8:3.8.

The preparation method of the above-mentioned low-aldehyde content slow-rebound polyurethane foam is carried out according to the following steps: successively add diethanolamine, triethylenediamine, foam stabilizer silicone oil L626, and cell opener GK-350D to the polyether polyol 300N , glycerol, lactic acid and deionized water, after stirring evenly, place in the mold, then add L-lysine, adipic acid dihydrazide and nitrile acetamide in sequence, then add isocyanate, at 670r/min Mechanically stir with an electric stirrer for 27s, until it is foamed and matured.

Comparative Example 1:

Raw materials for polyurethane preparation

Polyol A: polyether alcohol based on ethylene oxide and propylene oxide with an OH number of 28 mg KOH/g and a functionality of 2.7, with a propylene oxide content of 84% by weight and an ethylene oxide content of 14% by weight

Polyol B: polyether alcohol with an OH number of 250 mg KOH/g and a functionality of 2.0 based on polyol A (35%), propylene oxide (45%) and dimethylaminopropylamine (20%)

TEOA: Triethanolamine

Isopur SU-12021: Black paste available from ISL-Chemie

Jeffcat ZF10: Catalyst from Huntsman

Jeffcat DPA: Catalyst from Huntsman

Isocyanate component A: a mixture of 85 parts of carbodiimide-modified 4,4'-MDI and 15 parts of polymerized diphenylmethane diisocyanate PMDI, wherein the NCO content is 27.1;

Mixture A is prepared by mixing the following components:

92.4 parts by weight of polyol A

3.0 parts by weight of Polyol B

1.5 parts by weight of TEOA

0.5 parts by weight of Isopur SA-21050

1.9 parts by weight of water

0.4 parts by weight Jeffcat DPA

0.2 parts by weight of Jeffcat ZF10

0.55 parts by weight of sodium sulfite

The mixture A and the isocyanate component A were mixed with each other at an isocyanate index of 100 and charged into a closed mold to obtain a molding having an average density of 160 g/L.

Formaldehyde and acetaldehyde were determined by procedures based on ASTM D5116-06. The test chamber measures 4.7 liters. The polyurethane samples used were blocks with dimensions of 110 mm x 100 mm x 25 mm. When testing the molded foam, the part made from the inside of the foam is used. During the test, the temperature of the test chamber was 65°C and the relative humidity was 50%. The air replacement rate was 3.0 liters per hour. An exhaust stream containing volatile aldehydes from polyurethane was passed through a cartridge containing silica coated with 2,4-dinitrophenylhydrazine for 120 minutes. The DNPH cartridge was then eluted with a mixture of acetonitrile and water. The formaldehyde and acetaldehyde concentrations of the eluate were determined by HPLC. The detection limit for formaldehyde emission from this device is ≤ 11 μg/m ³ and in the case of acetaldehyde emission the detection limit is ≤ 6 μg/m ³ .

Table 1: Aldehyde Values

Analysis Project Comparative Example 1 Example 3 Example 4 Example 5 Example 6 Example 7 Formaldehydeμg/m³ 52 35 28 twenty three 46 25 Acetaldehydeμg/m³ 454 27 32 twenty one 38 29

It can be seen from Table 1 that the aldehyde removal effect of the present invention is good and the harm is small.

Comparative Example 2: The raw materials are shown in Table 2. It was prepared by molding method. Polyether 1, polyether 2, polyether 3, polyether 4, water, silicone oil L-580, A1 and A33 were prepared into a combined polyether. The temperature of polyether and isocyanate is controlled at 25℃, pour isocyanate into polyether, stir at high speed with mechanical stirring for 6-8s, quickly pour the material into aluminum mold, mature in mold for 6min and then demould to obtain slow rebound product.

Table 2: Comparative Example 2 Raw Materials and Dosage

Table 3: Foam Properties

Analysis Project Comparative Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 rebound time S 7 10 9 8 7 12 Elongation at break% 118 147 175 162 138 157 Tensile strength kPa 116 181 164 175 132 149

It can be seen from Table 3 that the slow rebound effect of the present invention is good, and the tensile strength is strong.

Claims (10)

1. The slow rebound polyurethane foam with low aldehyde content is characterized in that the slow rebound polyurethane foam with low aldehyde content is prepared from the following raw materials: the foam material is prepared from polyether polyol 330N, diethanol amine, deionized water, triethylene diamine, a cell opener, lactic acid, glycerol, a foam stabilizer, isocyanate and an aldehyde remover.

2. The low-aldehyde content slow-resilience polyurethane foam according to claim 1, wherein the aldehyde removing agent is one or a combination of L-lysine, solid amine, adipic acid dihydrazide and nitriloacetamide.

3. The slow rebound polyurethane foam with low aldehyde content as claimed in claim 2, wherein the weight parts of the raw materials are as follows: 55-60 parts of polyether polyol 330N, 0.4-0.75 part of diethanolamine, 3-4.5 parts of deionized water, 0.5-0.8 part of triethylene diamine, 1-3 parts of a cell opener, 0.03-0.045 part of lactic acid, 0.3-0.6 part of glycerol, 0.4-0.65 part of a foam stabilizer and 32-38 parts of isocyanate; wherein the weight parts of the aldehyde removing agents are as follows: 1-4.2 parts of L-lysine, 1.5-2.6 parts of solid amine, 1.3-4.2 parts of adipic dihydrazide and 1.2-2.4 parts of cyanoacetamide.

4. The low-aldehyde slow-rebound polyurethane foam according to claim 3, wherein the low-aldehyde slow-rebound polyurethane foam is prepared from the following raw materials in parts by weight: 58 parts of polyether polyol 330N, 0.54 part of diethanol amine, 3.8 parts of deionized water, 0.56 part of triethylene diamine, 2.2 parts of a cell opener, 0.035 part of lactic acid, 0.5 part of glycerol, 0.45 part of a foam stabilizer, 34 parts of isocyanate, 1.2 parts of L-lysine, 1.7 parts of solid amine, 1.4 parts of adipic dihydrazide and 1.2 parts of cyanoacetamide.

5. The low-aldehyde slow-rebound polyurethane foam according to claim 3, wherein the low-aldehyde slow-rebound polyurethane foam is prepared from the following raw materials in parts by weight: 56 parts of polyether polyol 330N, 0.6 part of diethanol amine, 4 parts of deionized water, 0.58 part of triethylene diamine, 2.5 parts of a cell opener, 0.038 part of lactic acid, 0.55 part of glycerol, 0.48 part of a foam stabilizer, 36 parts of isocyanate, 1.5 parts of L-lysine, 1.85 parts of solid amine, 1.6 parts of adipic dihydrazide and cyanoacetamide: 1.4 parts.

6. The low-aldehyde content slow-resilience polyurethane foam according to any one of claims 1 to 5, wherein the mass ratio of the polyether polyol 330N to the isocyanate is (4.5-6): (2.4-3.8).

7. Low aldehyde content slow resilience polyurethane foam according to any of claims 1 to 5, characterized in that the mass concentration of lactic acid is between 85% and 90%.

8. The slow rebound polyurethane foam with low aldehyde content as claimed in any one of claims 1 to 5, wherein the foam stabilizer is silicone oil B8002, silicone oil B8715 or silicone oil L626.

9. The low aldehyde content slow recovery polyurethane foam according to any one of claims 1 to 5, wherein the cell opener is cell opener Y1900, cell opener GK-350D or cell opener GLK-15.

10. A process for the preparation of a low aldehyde slow recovery polyurethane foam as claimed in any one of claims 1 to 9, characterized in that the process is carried out by the following steps:

sequentially adding diethanol amine, triethylene diamine, a foam stabilizer, a cell opening agent, glycerol, lactic acid and deionized water into polyether polyol 330N, uniformly stirring, placing into a mold, then adding an aldehyde removing agent, adding isocyanate, mechanically stirring for 20-27 s at 600-670 r/min, and foaming and curing.