WO2017063255A1

WO2017063255A1 - Biomass-based polyurethane spray foam plastic and method for preparation thereof

Info

Publication number: WO2017063255A1
Application number: PCT/CN2015/096026
Authority: WO
Inventors: 崔爱华; 林永飞; 魏建辉
Original assignee: 江苏绿源新材料有限公司
Priority date: 2015-10-14
Filing date: 2015-11-30
Publication date: 2017-04-20
Also published as: CN105294989B; CN105294989A; CN106317365B; CN106317365A

Abstract

Disclosed is a biomass-based polyurethane spray foam plastic, characterized as a polyurethane spray produced through foam polymerization by mixing a white material component, prepared with at least one biomass-based polyether polyol as a raw ingredient, with an isocyanate component. The product of the present invention has a high content of biomass-based materials, and when used as insulation and water-proofing spray for walls and roofs, the foam material has similar performance to fully petroleum-based foams.

Description

Bio-based polyurethane spray foam plastic and preparation method thereof

[0001] The present invention relates to a polyurethane spray foam, and more particularly to a bio-based polyol preparation polyurethane spray foam and a process for the preparation thereof.

Background technique

[0002] Polyurethane rigid foam is widely used in many fields of the national economy such as refrigerators, freezers, cold storage plates, sandwich panels, pipe insulation, refrigerated containers, building energy conservation, etc. due to its excellent thermal insulation properties. Polyurethane spray foam molding is The two-component polyurethane foam composition is directly sprayed onto the surface of the object for foam molding, and has the advantages of: strong adhesion to the substrate; easy processing, no matter what shape surface can be formed by spraying to form a thermal insulation layer, thereby greatly improving Labor productivity; at the same time, it has the functions of waterproof, sound absorption and sound insulation.

[0003] A polyether compound of a prior art polyurethane rigid foam, whose main component is a petroleum-removed product, is a non-renewable resource, and has a complicated processing process, high cost, and environmental pollution, and its price is also Fluctuating with fluctuations in oil prices. Bio-based polyether polyols are polyol compounds synthesized from soybean oil, rapeseed oil, cottonseed oil or palm oil. They are environmentally friendly, renewable resources and have been industrially produced. From the perspective of environmental protection and resource recycling, the use of bio-based polyether polyols is the main direction of future research.

[0004] Since bio-based polyether polyols have a relatively large molecular weight and a low hydroxyl value, they are mainly used in the modification of soft foams and polyisocyanate foams in polyurethanes. There are still relatively few applications for rigid foams and sprayed polyurethanes with lower indices, or the introduction of bio-based polyether polyols, which still require a large amount of petroleum-based polyesters and polyester polyols. There is still a need for a polyurethane rigid foam in polyurethane spray foam that has both high levels of bio-based materials and similar performance characteristics to foams made from existing petroleum-based materials.

Summary of invention

technical problem

[0005] It is an object of the present invention to provide a bio-based material having a high content, which is applied to thermal insulation and water-repellent spraying of a wall or a roof, so that the foam has properties similar to those of foams produced from all petroleum-based materials. Bio-based polyurethane spray foam and preparation method thereof.

Problem solution

Technical solution

The technical solution of the present invention is:

[0007] A bio-based polyurethane spray foam, characterized in that a polyurethane spray composition white component prepared by using at least one bio-based polyether polyol as a raw material is mixed with an isocyanate component to be foamed and polymerized.

[0008] The composition of the polyurethane composite white material is a polyol component of at least one bio-based polyether polyol, an amine and/or metal salt catalyst, a physical and/or chemical foaming agent, and a foam stabilization And optional flame retardant. The bio-based polyol has a weight ratio of the entire polyol component of from 5 to 75%, preferably from 20% to 50%.

[0009] The bio-based polyether polyol can be produced from various bio-based materials, including but not limited to: soybean oil, jatropha oil, palm oil, corn oil, peanut oil, cottonseed oil, rapeseed oil, olive oil, and a mixture of them. A particularly preferred bio-based polyether polyol is a soybean oil polyol.

[0010] The isocyanate component is a crude polymerized diphenylformamidine diisocyanate (PMDI) or an improved crude polymethylene polyphenylene having an average functionality between 2. 5-3. The ratio of the mass ratio of the polyurethane component to the isocyanate component is 1: 1-1. 5, preferably a ratio of 1:1. The spray foam has an average density of from 30 to 80 kg/m ³ , preferably a density of from 35 to 55 kg/m ³ .

[0011] The catalyst for bio-based polyurethane spray foam comprises an amine and/or metal salt catalyst, wherein the amine catalyst is a tertiary amine catalyst including pentamethyldiethylenetriamine, N,N-dimethyl ring One or more of hexylamine, triethylenediamine, triethylamine, and didimethylaminoethyl ether; the metal salt catalyst includes potassium isooctanoate, quaternary ammonium formate, potassium acetate, Two or more kinds of dibutyltin dilaurate, stannous octoate and potassium oleate. Since the polyurethane spray foam reacts very quickly, the solidification molding is normally completed in a dozen seconds. The amount of catalyst added is much larger than that required for other polyurethane foams, accounting for 5% to 15% of the polyurethane spray composition white component. The amount used.

[0012] A combination of water and a low boiling point compound is used as the blowing agent of the present invention. Low boiling point fluorine-containing compounds such as HFC-245fa, HFC-365mfc and HFC_134a, which are used singly or in combination. Particularly preferred blowing agents for use in the present invention are 1,1-dichloro-1-fluoroethane (HCFC-141B), 1, 1, 1, 3, 3_pentafluoropropene (HFC-245fa) and 1 1, 1, 3, 3-pentafluorobutyrate (HFC-365) and mixtures thereof. Normal anthraquinone blowing agent Because safety issues are rarely used in polyurethane spray foams, such as cyclopentamidine, isovalerone, and the like.

[0013] A small amount of foam stabilizer which is advantageous for foaming can be used in the polyurethane spray foaming to stabilize the foaming reaction mixture in the initial stage of polymerization, which helps to adjust the pore diameter and produce closed pores, thereby improving the heat insulating property. The foam stabilizer used is one or two of a non-hydrolyzed silicon-carbon surfactant and a non-silicone surfactant. Since the speed of spray foaming is rapid, the cells of the foam are relatively good. Therefore, the foam stabilizer used plays a more important role in the storage stability of the polyurethane sprayed white component before foaming.

[0014] Suitable flame retardants include phosphonates/salts, phosphites/salts and phosphates/salts (eg, dimethyl methylphosphonate, ammonium polyphosphate, and various cyclic phosphates and phosphonates) It is applied to bio-based polyurethane spray foam. Since polyurethane spray foam molding is formed by atomization and mixing foaming of foaming gun head, when flame retardant is selected, it is more liquid-oriented and has relatively good storage stability. Such as tris(2-chloroethyl) phosphate (TCEP), tris(2-chloropropyl) phosphate (TCPP), triethyl phosphate (TEP) and dimethyl methylphosphonate (DMMP) Or more, among which tris(2-chloropropyl)phosphate (TCPP) and triethyl phosphate (TEP) are preferred.

[0015] The preparation method of the bio-based polyurethane spray foam comprises the following steps: (1) mixing a polyol combination, a catalyst, a foaming agent, a foam stabilizer and an optional flame retardant in a ratio, thereby preparing Polyurethane composite white component; (2) The combined white component and the isocyanate component obtained in the step (1) are sprayed on a wooden board or a cement board by a high-pressure sprayer at a fixed ratio, and the two components are rapidly reacted and solidified. Formed to form a bio-based polyurethane spray foam.

Advantageous effects of the invention

Beneficial effect

[0016] The product of the present invention has a high content of bio-based material for use in thermal insulation and water-repellent spraying of walls or roofs, so that the foam has properties similar to those produced with all petroleum-based materials.

BEST MODE FOR CARRYING OUT THE INVENTION

[0017] The invention is further illustrated by the following examples, but the invention is not limited to the following examples, unless otherwise indicated, all amounts given by "parts" and "percents" should be understood as being by weight. of. The following materials were used to produce the polyurethane foam of the examples: [0018] Table 1 Introduction to Polyurethane Raw Materials

[]

[Table 1] No. Material Remarks

1 polyether polyol A sucrose starting refined polyether polyol, hydroxyl value 380mgK0H / g, viscosity at 25 ° C is about 10000 centipoise, hydroxyl functionality is 6;

2 polyether polyol B ethylenediamine starting polyether polyol, hydroxyl value 760mgK0H / g, viscosity at 25 ° C is about 25000 centipoise, hydroxyl functionality is 4;

3 flame retardant polyether polyol C bromine-containing flame retardant polyether polyol, hydroxyl value 200mgK0H / g, viscosity at 25 ° C is about 15000 centipoise, hydroxyl functionality is 2;

4 Polyester polyol D phthalate aromatic polyester polyol, hydroxyl value 310mgK0H / g, viscosity at 25 ° C is about 3000 centipoise, functionality is 2;

5 bio-based polyol E epoxidized soybean oil-based vegetable oil polyol, hydroxyl value 380mgK0H / g, viscosity at 25 ° C is about 5000 centipoise, the functionality is 4. 5;

6 Bio-based polyol F vegetable oil polyol, hydroxyl value 60mg

KOH/g, viscosity at 25 ° C of about 600 cps, functionality of 3, according to Chinese patent application number 201110 054557. X 7 Catalyst A pentamethyldiethylenetriamine

8 Catalyst B Triethylenediamine

9 Catalyst c Dibutyltin dilaurate

10 Foam Stabilizer Silicon Oxide Surfactant

11 flame retardant A tris(2-chloropropyl) phosphate (

TCPP)

12 Flame Retardant B Triethyl Phosphate (TEP)

13 blowing agent 1, 1-dichloro-1-fluoroacetamidine (HCFC

-141B)

14 Isocyanate Polymerized diphenylformamidine diisocyanate (PMDI), NC0 content of about 32. 4, viscosity at 25 ° C is about 25 centipoise

[0019] The components in the parts by weight listed in Table 2 below were mixed, and the weight ratio of the isocyanate component to the white component was 1:1, resulting in a free-foamed foam. These foams were prepared using a manual mixing procedure known to those skilled in the art to determine foam properties after the foam was cured.

Table 2 Polyurethane Foam Group Distribution Parameters (Parts by Weight)

[]

Actually, the example is fine and detailed.

1 2 3 4 5 6 7 S

1 Separation A 25 25 25 25 25 25 25

2 鲥Multi 15 15 15 15 15 15 15 20

Hj^lSl multiple

3 10 10 10 10 10 10 10 Vine C

4 50 10 10 20

5 50 40 35 49 40 20

E

6 10 15 10

¥

7 2 2 2 2 2 2 2 2

S 23 25 25 25 25 23 25 25

9 1 1 1 1 1 I I 1

10 25 25 25 25 25 25 25 25

11 15 15 15 15 15 15 35 35

12 10 10 10 10 10 10

Ϊ3 water iJ» LO 13 1J3 LO iJO LO ID

H 25 25 25 25 25 20 20 20

15 159 m 150 150 ISO 159 15» 150 Reference example 1 is a common formulation for polyurethane spray foams used in GB50404-2007. In an embodiment, the moiety is replaced with one or two bio-based polyols. If you want to adjust the foaming speed, you can adjust the amount of catalyst; if you want to adjust the foam density, you can adjust the amount of water and physical foaming agent.

Comparing the key foam properties such as density, thermal conductivity, and oxygen index with the control foam, some are better or worse. However, the most suitable original ratio can be achieved by adjusting the ratio of each compound, the performance is up to standard, the cost is optimized, and the bio-based polyether polyol is used in the best amount.

Table 3 Performance parameters of spray foam

As can be seen from Table 3, the bio-based polyol is combined with an aliphatic polyol to ensure the basic properties of the polyurethane spray foam and maximize the amount of bio-based polyol in combination with a high-functionality aliphatic polyol. At the same time, when using different bio-based polyols, different amounts should be used according to the characteristics of different products. Select Example 4 to carry out on-site foaming, and prepare the polyurethane sprayed white component according to Table 2, and then spray the prepared white component and isocyanate component in a fixed ratio on a wooden board by a high-pressure sprayer. The reaction solidifies and forms a bio-based polyurethane spray foam. The foam properties obtained by the foaming mechanism are better than the laboratory foaming properties.

The foregoing embodiments of the invention have been presented for purposes of illustration It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. The scope of the invention is defined by the appended claims.

Claims

Claim

[Claim 1] A bio-based polyurethane spray foam, characterized in that: a polyurethane spray composition white component prepared from at least one bio-based polyether polyol is mixed with an isocyanate component to form a foaming polymerization.

[Claim 2] The bio-based polyurethane spray foam according to claim 1, wherein: the at least one bio-based polyether polyol is prepared by using at least one component of the polyurethane sprayed composite white material. A polyol component of a bio-based polyether polyol, an amine and/or metal salt catalyst, a physical and/or chemical blowing agent, a foam stabilizer, and optionally a flame retardant.

[Claim 3] The bio-based polyurethane spray foam according to claim 2, wherein: the weight ratio of the bio-based polyol in the polyol component of the at least one bio-based polyether polyol is 5 -75%.

[Claim 4] The bio-based polyurethane spray foam according to claim 1, 2 or 3, wherein: the bio-based polyether polyol is selected from the group consisting of soybean oil, jatropha oil, palm oil, and corn oil. , peanut oil, cottonseed oil, rapeseed oil, olive oil or a mixture thereof.

The polymerization between 2. 5-3. 5 is more than 5. 5-3. 5。 The phenyl polyisocyanate; the ratio of the mass ratio of the polyurethane component to the isocyanate component is 1: 1-1.

[Claim 6] The bio-based polyurethane spray foam according to claim 1, wherein: the spray foam has an average density of 30 to 80 kg/m ³ .

[Claim 7] The bio-based polyurethane spray foam according to claim 2, wherein: the amine catalyst in the amine and/or metal salt catalyst is a tertiary amine catalyst including pentamethyldivinyl Two or more kinds of triamine, N,N-dimethylcyclohexylamine, triethylenediamine, triethylamine, didimethylaminoethyl ether; the metal salt catalysts include Two or more kinds of potassium octoate, quaternary ammonium formate, potassium acetate, dibutyltin dilaurate, stannous octoate and potassium oleate; the physical foaming agent is water; the chemical foaming agent One or more of 1,1-dichloro-1-fluoroethane, 1, 1, 1, 3, 3-pentafluoropropane, 1, 1, 1, 3, 3-pentafluoropyrene .

[Claim 8] The bio-based polyurethane spray foam according to claim 2, wherein: the foam stabilizer is one of a non-hydrolyzed silicon-carbon surfactant and a non-silicone surfactant or Two; the flame retardant is one or more of tris(2-chloroethyl)phosphate, tris(2-chloropropyl)phosphate, triethyl phosphate and dimethyl methylphosphonate .

[Claim 9] A method for preparing a bio-based polyurethane spray foam according to claim 1, comprising the steps of: (1) combining a polyol, a catalyst, a foaming agent, a foam stabilizer, and The flame retardant is uniformly mixed in proportion to obtain a polyurethane spray composition white component; (2) the combined white component and the isocyanate component obtained in the step (1) are sprayed at a fixed ratio through a high pressure spray machine. On the wood or cement board, the two components are rapidly reacted and solidified to form a bio-based polyurethane spray foam.