KR20120053748A - Enviromental-friendly polyurethane using biopolyol - Google Patents

Abstract

PURPOSE: Environmental-friendly polyurethane foam is provided to have excellent sound-absorbing properties in low density, and to satisfy physical properties of a product even in low density. CONSTITUTION: Polyurethane foam is foamed from 100.0 parts by weight of polyol mixture and 150-250 parts by weight of polyisocyanate by water. The polyol mixture comprises 5-40 weight% of biopolyol of which OH-V is 300-350, 30-90 weight% of trifunctional polyether polyol of which OH-V is 25-600, and 5-30 weight% of tetrafunctional or polyfunctional of which OH-V is 300-700. The biopolyol is polyol manufactured by using palm oil and having OH-V of 315-330. The trifunctional polyester polyol is a mixture of polyester polyol of which OH value is 20-50 and polyester poly of which OH value is 300-600.

Description

Eco-Friendly Polyurethane Foam Using Bio Polyol and Manufacturing Method Thereof {ENVIROMENTAL-FRIENDLY POLYURETHANE USING BIOPOLYOL}

The present invention relates to an environment-friendly polyurethane foam and a method for manufacturing the same, and more particularly, to manufacture a polyurethane foam using a naturally derived polyol, and to apply it to a new product that can be used industrially, in particular in the headliner of automobiles It relates to a method for producing a polyurethane foam that can be used.

As the environment emerges as a topic of humanity, efforts are being made to convert many items into environmentally friendly materials in various places of life. In developed countries, eco-friendly materials that consider the environment and health are already closely related to daily life, but Korea is still in the beginning stage. However, Korea is also developing eco-friendly products in various fields. Recently, the case of developing and applying interior materials of eco-friendly materials to the automobile industry is increasing. Accordingly, a method for producing polyurethane using environmentally friendly raw materials has been developed.

In many patents, including US Pat. Nos. 6,180,686, 6,465,569, and 6,624,244, Kurth discloses the use of unmodified (oxidized) soybean oils as polyols in the production of polyurethane materials.

Korean Patent Publication No. 10-2006-0107330 discloses a method for preparing a polyurethane foam by mixing soybean oil-modified alkoxylated vegetable oil hydroxylate with a non-vegetable oil.

However, these soybean-derived polyols are limited in their replacement for products requiring demanding properties.

For example, in case of head-liner used as a ceiling material inside a car, it should be excellent in formability to fit various shapes of the car while maintaining the rigidity enough to maintain the interior ceiling shape of the car, and the shape without deformation after installation. It is a field where demanding characteristics are required, such as maintaining excellent sound insulation while maintaining.

Conventionally, the basic patents of domestic car head-liner include Korean Patent No. 178401 (Registration Date 1998.11.23) and Korean Patent 412228 (Registration Date 2003.12.10). Bubble rigid polyurethane foam has a problem that the mixing of the raw stock solution is complicated and expensive, and there is a problem of lowering the adhesive strength of the skin and nonwoven fabric due to the generation of polyurethane powder when cutting the foam to a certain thickness, According to the development of the automobile industry, foamed polyurethane in Korean Patent No. 178401 according to Korean Patent No. 178401 shows a limitation in size to be applied to various sizes of products by molding in a mold mold. There are disadvantages.

In addition, in the case of polyurethane, various kinds of low boiling point organic compounds are used. In the case of continuous bubble rigid foams which are easy to hot-form in Korean Patent No. 412228, water and methylene chromide are used as polyurethane foaming agents. Methylene chloride is known to be harmful to the human body, and some of the low-boiling methylene chloride volatilizes when polyurethane is foamed, but remains in the rigid foam of continuous bubbles, and various reinforcement materials are used by foaming foamed with methylene chloride. When the product is thermoformed and mounted on a vehicle, it gradually escapes from the foam of the molded foam as the temperature inside the vehicle rises, which may cause deformation (embossing) of the structure of the automobile molding, but especially methylene chloride harmful gas Get out of the bubble and water for the driver It can act as.

In addition, in the case of Korean Patent Nos. 178401 and 412228, ester-based polyols are used. Polyester polyols have hydrophilicity, and polyether polyols have hydrophobicity and thus have low compatibility. As a result, there may occur a problem of storage stability in which separation occurs between the polyester polyol and the polyether polyol layer, and Korean Patent No. 412228 has a disadvantage of using methylene chloride, which is harmful to the human body, as a blowing agent.

Accordingly, there is a continuing need for a new method that can be used in fields requiring complex physical properties or processability, such as headliners of automobiles, by using naturally derived eco-friendly polyols.

  An object of the present invention is to produce an eco-friendly polyurethane foam that satisfies the mechanical properties of the product even at a low density and environmentally friendly by applying an eco-friendly bio polyol

Is to provide a way.

Another object of the present invention is to provide a method of making a polyurethane foam using only low-cost water by performing polyurethane foaming without using a low boiling point organic compound blowing agent used in polyurethane foaming.

Another object of the present invention is to provide a method of making a polyurethane foam capable of intermittent foaming to suit various sizes and shapes of automobiles.

Another object of the present invention is to provide an intermittent polyurethane foam that is applicable to automotive parts (eg automotive headliners).

The present invention is 5 to 40% by weight of a bio polyol having an OH-V of 300 to 350; 30 to 90 wt% of a trifunctional polyether polyol having an OH-V of 25 to 600; It consists of an intermittent polyurethane foam characterized by foaming water with 100 parts by weight of mixed polyol consisting of 5-30% by weight of 4 or more high-functional polyetherpolyols of OH-V 300-700 and 150-250 parts by weight of polyisocyanate.

In the present invention, the bio polyol is a plant-derived polyol, natural polyol or modified polyol can be used. Preferably a polyol having OH-V of 315-330 prepared using palm oil. In the practice of the invention, the polyol prepared using the palm oil can be purchased commercially and used, the product is OH-V is 315-330 measured by the end group analysis prepared by Maschima, Indonesia, end group The molecular weight measured by the assay corresponds to about 280-7000.

In the present invention, the trifunctional polyether polyol has a low OH-V polyether polyol having a OH value of 100 or less, preferably about 20-50, more preferably 25-30, and an OH value of about 300 A mixture of polyether polyols of high OH-V value which is -600, preferably 330-360.

In one preferred embodiment of the present invention, the trifunctional polyether polyol having a low OH-V value can be obtained by addition polymerization of a trihydric alcohol such as glycerin, trimethylol propane with ethylene oxide and propylene oxide. It is a functional polyether.

In a preferred embodiment of the present invention, the high functional OH-V trifunctional polyether polyol is a trifunctional polyether obtained by addition polymerization of a trihydric alcohol such as glycerin and trimethylol propane with propylene oxide. .

In a preferred embodiment of the invention, the low OH-V value trifunctional polyether polyol and the high OH-V value trifunctional polyether polyol have a weight ratio of 2: 8 to 8: 2, preferably 3: 7. ~ 7: 3 is good to use.

In the present invention, at least four highly functional polyetherpolyols having an OH-V value of 300 to 700 can be obtained by addition polymerization of ethylene oxide and propylene oxide with a tetrahydric alcohol, such as ethylene diamine, toluene diamine, pentaerythritol. Tetrafunctional polyether. The OH values of these polyethers are from 300 to 700, which generally correspond to about 3000 to 6400 molecular weight as determined by terminal group analysis. In a preferable embodiment, one or more of the above-mentioned high functional polyether polyols can be selected from 4 to 6 functional polyols.

In the present invention, if the content of the high functional polyol of 4 or more is excessively increased, the foam growth of the foam is lowered with increasing viscosity, the workability is lowered, and if the content of the high functional polyol is reduced, polyurethane Problems can arise in the physical dimensional stability of the foam after foaming.

In the practice of the present invention, the polyurethane foam is about 2 to 10 parts by weight of a cell opener, 0.5 to 2 parts by weight of a silicone foam stabilizer, and 2 to 100 parts by weight of mixed polyol so as to be suitable for the process of intermittent polyurethane foaming. It is a 10 weight part crosslinking agent, and can be manufactured using 6-8 weight part of water and 0.5-2 weight part of catalysts as a blowing agent.

In the present invention, the cell opener is a trifunctional hydroxyl polyether having an OH value of about 30 to 400, and an addition polymerization reaction of ethylene oxide and propylene oxide with a trihydric alcohol (eg, glycerine, trimethylol propane, etc.). Trifunctional polyethers. The OH values of these polyethers range from 30 to 400, which generally correspond to about 420 to 5610 molecular weight, as determined by terminal group analysis.

In the present invention, the crosslinking agent is a 2-3 functional crosslinking agent such as ethylene glycol, propylene glycol, dieterene glycol, dipropylene glycol, butanediol, trimethelol propane, 1.3 butane diol, 1,4 butane diol and the like are used. .

In the present invention, the crosslinking agent may be optionally added to control the physical properties of the polyol, and when the amount of the crosslinking agent component increases, the physical properties of the crosslinking agent are increased by increasing the crosslinking density of the polyurethane foam. If the content is too high, there may be a problem in the stability of the entire polyol system.

In the present invention, it is used as a foaming agent so that it is harmless even if it escapes from the foaming cell when used in an environment-friendly foaming environment of water and a vehicle.

The catalyst used in the present invention is a tertiary amine which can be incorporated into a polyol group.

In the case of amines, odors are produced after they are made of automotive interior materials, which not only harms the driver's health but also affects automotive interior components. To solve this problem, a tertiary amine, but using a self-reactive catalyst, is used. It is preferable. Catalysts having self-reactivity are brand names AIR-PRODUCT DABCO BL-11, TOYOCAT HX-35, HX-63, RX-20, RX-21, HUNTSMAN JEFFCAT ZF-10, ZF-22, ZR-70, DPA, etc. can be used.

In the present invention, the polyisocyanate component comprises about 70 to about 90 weight percent of the fraction containing two nuclei (about 12 to about 30 weight percent thereof, preferably about 15 to 24 weight percent is 2.4 ' Diphenyl methane diisocyanate). A fraction containing three or more nuclei is MDI, which constitutes about 10-30% by weight. Preferably, fractions containing four or more nuclei are present at 3% by weight or less. Particular preference is given to MDIs having the fractions in Table 1 below.

2 core content: 74% by weight

content rescue 52 wt% Diphenyl Methane 4.4'-Diisocyanate 19% by weight Diphenyl Methane 2.4'-Diisocyanate 3 wt% Diphenyl Methane 2.2'-Diisocyanate

-3 core + 4 core content: 23% by weight

-The rest (more than 4 nuclei): 3% by weight

In the present invention, other additives (flame retardants, plasticizers, fillers, antibacterial agents, pigments, dyes, etc.) may be added according to the production and required physical properties to produce a foam.

The foam prepared according to the present invention can be used to prepare a polyol component and a polyisocyanate component in a weight ratio of polyol to isocyanate up to 100: 150-200, preferably about 100: 170-190 by mixing in a weight ratio. It is good.

The foams produced according to the invention are usually from 20 to 30 kg / m 3, preferably from 20 to 24 kg / m 3.

In another aspect, the present invention provides a OH-V of 5 to 40% by weight of a bio polyol having 300 to 350; 30 to 90 wt% of a trifunctional polyether polyol having an OH-V of 25 to 600; 100 parts by weight of polyol consisting of 5-30% by weight of 4 or more high-functional polyether polyols of OH-V 300-700 and 150-250 parts by weight of polyisocyanate are intermittently foamed with water to have a molding density of 20-24 Kg / m 3 Provided is a method of making a urethane foam.

Bio-polyols and polyether polyols produce polyurethane intermittent rigid foams, and products can be manufactured only with polyether polyols, and there is no problem of separation or miscibility when using polyester polyols and hydrolysis problems. Without intervening, it is possible to produce an intermittent rigid urethane foam having excellent foam mechanical properties while foaming only with environmentally friendly water.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail. The contents described herein are for illustrating the present invention and are not intended to limit the invention.

Item ingredient Example 1 Example 2 Example 3 Example 4 pole
Lee
Come

wife
room Bio polyols 1 10 15 20 30 Polyol 2 40 35 30 20 Polyol 3 40 40 35 35 Polyol 4 10 10 15 15 Silicone foam stabilizer 2 2 2 2 Crosslinking agent 1 4 4 4 4 Crosslinking agent 2 2 2 2 2 Cell-opener 4 4 4 4 Catalyst 1 0.15 0.15 0.15 0.15 Catalyst 2 0.5 0.5 0.5 0.5 water 6.8 6.8 6.8 6.8 half
Huh
castle C / T 40 40 42 41 G / T 160 163 165 165 H / B 198 205 209 211 FRD 26-30 26-30 26-30 26-30 Molding density 20 to 24 20 to 24 20 to 24 20 to 24 water

castle Elongation % 16 to 20 16 to 20 16 to 20 16 to 20 Compressive strength kPa 36 to 40 36 to 40 36 to 40 36 to 40 Flexural strength Mpa 2.2 to 2.8 2.2 to 2.8 2.2 to 2.8 2.2 to 2.8

In the above table, the biopolyol is a polyol prepared using palm oil in the following examples, polyol 2 is a propylene oxide initiated glycerin with a trifunctional polyetherpolyol of high OH-V, and polyol 3 is low OH- It is propylene oxide / ethylene oxide which started glycerin with trifunctional polyether polyol of V, and polyol 4 is propylene oxide which pentaerythritol was opened with tetrafunctional polyether polyol.

160 parts by weight of polyphenyl polymethylene having about 12% polyisocyanate component polyisocyanate (diphenyl methane 2.4'- diisocyanate isomer content is about 20%, NCO content is 31.7 to 32.4%, viscosity at 25 ℃ Is about 50-100cps)

100 parts by weight of the polyol component (including water) has a mixed OH value of 620. 100 parts of the polyol component is combined with 180 parts by weight of polyisocyanate, the index (ratio of isocyanate to hydroxyl group) is 110 when the total water content is stoichiometrically included.

Hereinafter, the present invention will be described in detail with reference to Examples.

Example 1

OH-V value 320 8.37 parts by weight

33.5 parts by weight of propylene oxide starting glycerin

(Polyether OH value 350)

33.5 parts by weight of propylene oxide / ethylene oxide starting glycerin

  (Polyether OH value 28)

8.4 parts by weight of propylene oxide with pentaerythritol

(Polyether OH value 410)

3.4 weight part of propylene oxide / ethylene oxide which started glycerin

(Cell Opener of Polyether OH Value 330)

3.4 weight part of crosslinking agent 1

1.7 parts by weight of crosslinking agent 2

OH value 6222 5.7 parts by weight

1.7 parts by weight of silicone foam stabilizer

0.54 parts by weight of catalyst

Example 2

OH-V value 320 12.6 parts by weight

29.3 parts by weight of propylene oxide initiating glycerin

(Polyether OH value 350)

33.5 parts by weight of propylene oxide / ethylene oxide starting glycerin

  (Polyether OH value 28)

8.4 parts by weight of propylene oxide with pentaerythritol

  (Polyether OH value 410)

3.4 weight part of propylene oxide / ethylene oxide which started glycerin

Cell opener (of polyether OH value 330)

3.4 weight part of crosslinking agent 1

1.7 parts by weight of crosslinking agent 2

OH value 6222 5.7 parts by weight

1.7 parts by weight of silicone foam stabilizer

0.54 parts by weight of catalyst

Example 3

OH-V value 320 16.7 parts by weight

25.1 parts by weight of propylene oxide starting glycerin

(Polyether OH value 350)

29.3 parts by weight of propylene oxide / ethylene oxide starting glycerin

  (Polyether OH value 28)

12.6 parts by weight of propylene oxide starting pentaerythritol

  (Polyether OH value 410)

3.4 weight part of propylene oxide / ethylene oxide which started glycerin

Cell Opener Of Polyether OH Value 330

3.4 weight part of crosslinking agent 1

1.7 parts by weight of crosslinking agent 2

OH value 6222 5.7 parts by weight

1.7 parts by weight of silicone foam stabilizer

0.54 parts by weight of catalyst

Example 4

OH-V value 320 25.1 parts by weight prepared with palm oil

16.7 parts by weight of propylene oxide starting glycerin

(Polyether OH value 350)

29.3 parts by weight of propylene oxide / ethylene oxide starting glycerin

  (Polyether OH value 28)

12.6 parts by weight of propylene oxide starting pentaerythritol

(Polyether OH value 410)

3.4 weight part of propylene oxide / ethylene oxide which started glycerin

Cell opener of (polyether OH value 330)

3.4 weight part of crosslinking agent 1

1.7 parts by weight of crosslinking agent 2

OH value 6222 5.7 parts by weight

1.7 parts by weight of silicone foam stabilizer

0.54 parts by weight of catalyst

Claims (10)

5 to 40% by weight of a bio polyol having an OH-V of 300 to 350; 30 to 90 wt% of a trifunctional polyether polyol having an OH-V of 25 to 600; OH-V Polyurethane foam characterized by foaming water with 100 parts by weight of mixed polyol consisting of 5 to 30% by weight of 4 or more high-functional polyether polyol up to 300 to 700 and 150-250 parts by weight of polyisocyanate. The polyurethane foam according to claim 1, wherein the bio polyol is a polyol having an OH-V of 315-330 prepared using palm oil. The polyfunctional polyol of claim 1 wherein the trifunctional polyether polyol is a mixture of a low OH-V polyether polyol having an OH value of 20-50 and a high OH-V polyether polyol having an OH value of 300-600. Polyurethane foam, characterized in that. The polyfunctional polyether polyol of claim 3, wherein the trifunctional polyether polyol having a low OH-V value is a polyol obtained by addition polymerization of a trihydric alcohol with ethylene oxide and propylene oxide, and the trifunctional polyether polyol having a high OH-V value is Polyurethane foam which is a polyol which trivalent alcohol addition-polymerized by propylene oxide. The polyurethane foam according to claim 1, wherein the four or more highly functional polyether polyols are four to six functional polyols obtained by addition polymerization of ethylene oxide and propylene oxide with a 4-6 valent alcohol. The polyurethane foam according to any one of claims 1 to 5, wherein the polyurethane foam is about 2 to 10 parts by weight of a cell opener, 0.5 to 2 parts by weight of a silicone foam stabilizer and 2 to 10 parts by weight of a crosslinking agent based on 100 parts by weight of the total polyol. Polyurethane foam, characterized in that 6 to 8 parts by weight of water and 0.5 to 2 parts by weight of catalyst as a blowing agent. 7. The polyurethane foam of claim 6 wherein the cell opener is a trifunctional hydroxyl polyether having an OH value of about 30 to 400. The rigid urethane foam according to any one of claims 1 to 5, wherein a molding density of the intermittent hard urethane is 20 to 24 Kg / m 3. The rigid urethane foam according to any one of claims 1 to 5, wherein the polyurethane foam is a headliner foam. 5 to 40% by weight of a bio polyol having an OH-V of 300 to 350; 30 to 90 wt% of a trifunctional polyether polyol having an OH-V of 25 to 600; 100 parts by weight of polyol consisting of 5-30% by weight of 4 or more high-functional polyether polyols of OH-V 300-700 and 150-250 parts by weight of polyisocyanate are intermittently foamed with water to have a molding density of 20-24 Kg / m 3 Method of making urethane foam.