CN104194319B - A kind of halogen-free high flame-retardant polyisocyanurate foam and preparation method thereof - Google Patents

Abstract

The invention discloses a halogen-free highly flame-retardant polyisocyanurate foam and a preparation method thereof, which is characterized in that: the weight ratio of each raw material in the foam is: polyisocyanurate foam raw material 65-95% ; hypophosphite flame retardant 5-15%; ammonium polyphosphate flame retardant 0-10%; organic phosphorus-containing flame retardant 0-10%; polyisocyanurate foam raw materials are polyester polyols, amines Catalyst, metal catalyst, water, polysiloxane foam stabilizer, physical blowing agent and polyisocyanate. The halogen-free highly flame-retardant polyisocyanurate foam obtained in the present invention integrates condensed phase flame retardancy and gas phase flame retardancy, and has high flame retardancy, good mechanical properties and thermal insulation performance.

Description

A kind of halogen-free highly flame-retardant polyisocyanurate foam and its preparation method

technical field

The invention belongs to the technical field of flame retardants, and in particular relates to a halogen-free highly flame-retardant polyisocyanurate foam and a preparation method thereof.

Background technique

The frequent occurrence of high-rise building fires has brought serious losses to the country and the people, mainly due to the flammable external wall insulation materials. How to improve the flame retardancy of external wall insulation materials has become an urgent problem to be solved. Rigid polyurethane foam has excellent characteristics such as good thermal insulation effect, light weight, high specific strength, and convenient construction. It is widely used in buildings, storage tanks and pipeline insulation materials. Polyurethane foam board is mainly divided into rigid polyurethane foam board (RPUF) and polyisocyanurate foam board (PIR). Polyisocyanurate foam has a higher flame retardancy than ordinary rigid polyurethane foam due to its stable six-membered ring of isocyanurate.

The national standard GB8624-2012 (classification of combustion performance of building materials and products) stipulates that in order to make wall insulation foam plastics meet the requirements of B1 level (flammable materials), the limiting oxygen index LOI of foam plastics is required to be ≥ 30. Class B2 (flammable materials) limiting oxygen index LOI ≥ 26.

Because polyisocyanurate foam contains a large number of isocyanurate six-membered rings in its structure, it is easier to flame-retardant than general rigid polyurethane foam, especially polyisocyanurate containing aromatic ring polyester structure Foam, only a small amount of flame retardant can be added to reach B2 level. However, there are few reports meeting the B1 flame retardant requirements.

Chinese patent CN103665305A discloses a high flame-retardant polyisocyanurate rigid foam and a preparation method thereof, in which phosphorus-containing chlorine-containing liquid flame retardants (such as tris(2-chloroethyl) ester (TCEP) are mainly used ), tris(2-chloropropyl) phosphate (TCPP), etc.), phosphorus-containing liquid aromatic flame retardant and solid microencapsulated red phosphorus flame retardant, the highest oxygen index can reach more than 30; Chinese patent CN102391465A discloses A polyisocyanurate combination material for high flame-retardant boards and a preparation method thereof, in which aromatic polyester polyols and phosphorus- and chlorine-containing liquid flame retardants such as TCPP and TCEP are mainly used, and the highest oxygen index can reach more than 34. However, halogen-containing flame retardants are all used in said patents. Although these flame retardants have high flame retardant efficiency, they will release corrosive and toxic smoke during the combustion process, which is seriously destructive to surrounding building facilities and may cause secondary disasters. Toxic fumes are extremely harmful to humans. There are few reports on polyisocyanurate foams that only use halogen-free phosphorus-containing flame retardants to meet the requirements of B1 flame retardancy.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies in the prior art, to provide a kind of halogen-free highly flame-retardant polyisocyanurate foam and its preparation method, the prepared polyisocyanurate foam oxygen index can reach 30, Therefore, the use of halogen-containing flame retardants is avoided, and at the same time, it has good thermal insulation and mechanical properties.

For solving the problems referred to above, the technical scheme that the present invention takes is:

The halogen-free highly flame-retardant polyisocyanurate foam of the present invention is characterized in that: the weight ratio of each raw material in the foam is: polyisocyanurate foam raw material 65% to 95%; hypophosphite flame-retardant 5-15% additive; 0-10% ammonium polyphosphate flame retardant; 0-10% organic phosphorus-containing flame retardant.

The halogen-free highly flame-retardant polyisocyanurate foam of the present invention is characterized in that: the polyisocyanurate foam raw material is composed of polyester polyol, amine catalyst, metal catalyst, water, polysiloxane Composition of similar foam stabilizers, physical blowing agents and polyisocyanates;

In the polyisocyanurate foam raw material, the mass ratio of polyester polyol, amine catalyst, metal catalyst, water, polysiloxane foam stabilizer, physical blowing agent and polyisocyanate is 100:1 -5:0.1-1:0.5-1.5:1-3:10-50:250-350.

The preparation method of the halogen-free highly flame-retardant polyisocyanurate foam of the present invention is characterized in that:

a. Weigh polyester polyol, amine catalyst, metal catalyst, water, polysiloxane foam stabilizer, physical blowing agent, polyisocyanate, hypophosphite, ammonium polyphosphate and organic phosphorus flame retardant constitute a raw material group;

b. Mix polyester polyol, amine catalyst, metal catalyst, water, polysiloxane foam stabilizer, physical blowing agent and organic phosphorus-containing flame retardant, and stir evenly to obtain mixture A;

c. Mix hypophosphite, ammonium polyphosphate and polyisocyanate, and mechanically stir evenly to obtain mixture B;

d. Add the mixture A obtained in step b to the mixture B obtained in step c, stir evenly and pour it into a mold for foaming. After the foam is initiated, take out the foam and place it in a 70-degree oven to mature for 24 hours, that is A halogen-free highly flame-retardant polyisocyanurate foam was obtained.

The mass ratio of polyester polyol, amine catalyst, metal catalyst, water, polysiloxane foam stabilizer, physical foaming agent, and polyisocyanate in the raw material group described in step a is: polyester polyol: amine Catalyst: metal catalyst: water: polysiloxane foam stabilizer: physical blowing agent: polyisocyanate = 100: 1-5: 0.1-1: 0.5-1.5: 1-3: 10-50: 250-350 The quality of hypophosphite is 5-15% of the total mass of the raw material group; the quality of ammonium polyphosphate is 0-10% of the total mass of the raw material group; the quality of the organic phosphorus-containing flame retardant is 0-10% of the total mass of the raw material group %.

Preferably, the polyester polyol is a phthalic anhydride polyester polyol with a hydroxyl value of 250-350 mgKOH/g;

The amine catalyst is one or a combination of Air Chemical Polycat 8 and Air Chemical Polycat 46.

The metal catalyst is one or both of Air Chemical Dabco K-15 and Air Chemical Polycat 46;

The polysiloxane foam stabilizer is polyether modified silicone oil;

The physical blowing agent is preferably monofluorodichloroethane (HCFC141b).

The polyisocyanate is a polymethylene polyphenyl polyisocyanate with a mass percentage of NCO groups of 30 to 32 wt %;

The hypophosphite is melamine hypophosphite, aluminum hypophosphite, calcium hypophosphite, cerium hypophosphite, zinc hypophosphite or lanthanum hypophosphite.

The ammonium polyphosphate is crystalline type II high-molecular-weight ammonium polyphosphate or microcapsule ammonium polyphosphate (such as melamine resin microcapsule ammonium polyphosphate, phenolic resin microcapsule ammonium polyphosphate and silica gel microcapsule) with a degree of polymerization n>1000. ammonium polyphosphate).

The organic phosphorus-containing flame retardant is resorcinol bis(diphenyl phosphate) (RDP), bisphenol A bis(diphenyl phosphate) (BDP), dimethyl methylphosphonate (DMMP) , diethyl ethyl phosphonate (DEEP), trimethyl phosphate (TMP), triethyl phosphate (TEP) or a mixture of several.

Compared with the prior art, the beneficial effects of the present invention are reflected in:

The flame retardant design of the present invention integrates condensed phase flame retardant and gas phase flame retardant as a whole, the raw materials are easy to obtain, the preparation is simple, the flame retardant efficiency is high, and the cost is low; the prepared polyisocyanurate foam has strong self-extinguishing property, which can reach UL-94V-0 level, good thermal insulation effect, good mechanical properties.

specific embodiment

The preparation method of the halogen-free highly flame-retardant polyisocyanurate foam of this embodiment is carried out according to the following steps:

a. Weigh polyester polyol, amine catalyst, metal catalyst, water, polysiloxane foam stabilizer, physical blowing agent, polyisocyanate, hypophosphite, ammonium polyphosphate and organic phosphorus flame retardant constitute a raw material group;

b. Mix polyester polyol, amine catalyst, metal catalyst, water, polysiloxane foam stabilizer, physical blowing agent and organic phosphorus-containing flame retardant, and stir evenly to obtain mixture A;

c. Mix hypophosphite, ammonium polyphosphate and polyisocyanate, and mechanically stir evenly to obtain mixture B;

d. Add the mixture A obtained in step b to the mixture B obtained in step c, stir evenly and pour it into a mold for foaming. After the foam is initiated, take out the foam and place it in a 70-degree oven to mature for 24 hours, that is A halogen-free highly flame-retardant polyisocyanurate foam was obtained.

The quality of each raw material in the raw material group is as shown in Table 1:

The formula of each raw material used in table 1 comparative example and embodiment 1-5

Note: The polyester polyol used in the comparative example is a phthalic anhydride polyester polyol with a hydroxyl value of 300mgKOH/g; the amine catalyst is a mixture of Air Chemical Polycat 8 and Air Chemical Dabco TMR-2 in a mass ratio of 1:1.5; metal Catalyst is Air Chemical Dabco K-15; water is deionized water; foam stabilizer is polyether modified silicone oil; physical foaming agent is fluorodichloroethane (HCFC141b); polyisocyanate is (NCO%=32%) Polymethylene polyphenyl polyisocyanates.

The polyester polyol used in Example 1 is a phthalic anhydride polyester polyol with a hydroxyl value of 330 mgKOH/g; the amine catalyst is a mixture of Air Chemical Polycat 8 and Air Chemical Dabco TMR-2 in a mass ratio of 1:2; the metal catalyst It is Air Chemical Industry Dabco K-15; Water is deionized water; Foam stabilizer is polyether modified silicone oil; Physical foaming agent is fluorodichloroethane (HCFC141b); Polyisocyanate is (NCO%=32%) Polymethylene polyphenyl polyisocyanate; hypophosphite flame retardant is melamine hypophosphite; ammonium polyphosphate flame retardant is crystalline type II high molecular weight ammonium polyphosphate with polymerization degree n>1000; organic phosphorus flame retardant It is trimethyl phosphate (TMP).

The polyester polyol used in Example 2 is a phthalic anhydride polyester polyol with a hydroxyl value of 280 mgKOH/g; the amine catalyst is a mixture of Air Chemical Polycat 8 and Air Chemical Dabco TMR-2 in a mass ratio of 1:3; the metal catalyst It is Air Chemical Polycat 46; water is deionized water; foam stabilizer is polyether modified silicone oil; physical blowing agent is fluorodichloroethane (HCFC141b); Methyl polyphenyl polyisocyanate; hypophosphite flame retardant is calcium hypophosphite; ammonium polyphosphate flame retardant is melamine resin microcapsule ammonium polyphosphate; organic phosphorus flame retardant is diethyl ethyl phosphonate ( DEEP).

The polyester polyol used in Example 3 is a phthalic anhydride polyester polyol with a hydroxyl value of 315 mgKOH/g; the amine catalyst is a mixture of Air Chemical Polycat 8 and Air Chemical Dabco TMR-2 in a mass ratio of 1:2.5; the metal catalyst It is Air Chemical Industry Dabco K-15; Water is deionized water; Foam stabilizer is polyether modified silicone oil; Physical foaming agent is fluorodichloroethane (HCFC141b); Polyisocyanate is (NCO%=32%) Polymethylene polyphenyl polyisocyanate; hypophosphite flame retardant is aluminum hypophosphite; ammonium polyphosphate flame retardant is crystalline type II high molecular weight ammonium polyphosphate with polymerization degree n>1000; organic phosphorus flame retardant is Dimethyl methylphosphonate (DMMP).

The polyester polyol used in Example 4 is a phthalic anhydride polyester polyol with a hydroxyl value of 300 mgKOH/g; the amine catalyst is a mixture of Air Chemical Polycat 8 and Air Chemical Dabco TMR-2 in a mass ratio of 1:2; the metal catalyst It is Air Chemical Industry Dabco K-15; Water is deionized water; Foam stabilizer is polyether modified silicone oil; Physical foaming agent is fluorodichloroethane (HCFC141b); Polyisocyanate is (NCO%=32%) Polymethylene polyphenyl polyisocyanate; hypophosphite flame retardant is lanthanum hypophosphite; ammonium polyphosphate flame retardant is phenolic resin microcapsule ammonium polyphosphate; organic phosphorus flame retardant is resorcinol bis(di phenyl phosphate) (RDP).

The polyester polyol used in Example 5 is a phthalic anhydride polyester polyol with a hydroxyl value of 330 mgKOH/g; the amine catalyst is a mixture of Air Chemical Polycat 8 and Air Chemical Dabco TMR-2 in a mass ratio of 1:3; the metal catalyst It is a mixture of Air Chemical Dabco K-15 and Air Chemical Polycat 46 in a mass ratio of 1:1; the water is deionized water; the foam stabilizer is polyether modified silicone oil; the physical blowing agent is a fluorodichloroethane (HCFC141b ); the polyisocyanate is (NCO%=32%) polymethylene polyphenyl polyisocyanate; the hypophosphite flame retardant is cerium hypophosphite; the ammonium polyphosphate flame retardant is silica gel microcapsule ammonium polyphosphate; The organic phosphorus-containing flame retardant is a mixture of dimethyl methylphosphonate (DMMP) and bisphenol A bis(diphenyl phosphate) (BDP) in a mass ratio of 2:1.

Table 2 shows the density, mechanical properties, thermal conductivity and flame retardancy of the polyisocyanurate foams prepared in Comparative Examples and Examples 1-5. It can be seen from the table that the halogen-free flame-retardant isocyanurate foam prepared by the present invention has good flame-retardant effect, good mechanical properties and thermal insulation properties.

Density, mechanical properties, thermal conductivity and flame retardancy of the polyisocyanurate foams prepared in Table 2 Comparative Examples and Examples 1-5

The present invention has been described in detail above, and its purpose is to allow those of ordinary skill in the art to understand the content of the present invention and implement it, and can not limit the protection scope of the present invention with this. All equivalent transformations should fall within the protection scope of the present invention.

Claims (5)

1. A halogen-free highly flame-retardant polyisocyanurate foam, characterized in that: the weight ratio of each raw material in the foam is: polyisocyanurate foam raw material 65% to 95%; hypophosphite Flame retardant 5-15%; ammonium polyphosphate flame retardant 0-10%; organic phosphorus-containing flame retardant 0-10%; and the quality of ammonium polyphosphate and organic phosphorus-containing flame retardant is not zero; The polyisocyanurate foam raw material is composed of polyester polyol, amine catalyst, metal catalyst, water, polysiloxane foam stabilizer, physical blowing agent and polyisocyanate; In the polyisocyanurate foam raw material, the mass ratio of polyester polyol, amine catalyst, metal catalyst, water, polysiloxane foam stabilizer, physical blowing agent and polyisocyanate is 100:1 -5:0.1-1:0.5-1.5:1-3:10-50:250-350. 2. The halogen-free highly flame-retardant polyisocyanurate foam according to claim 1, characterized in that: the polyester polyol is a phthalic anhydride polyester polyol with a hydroxyl value of 250-350 mgKOH/g; The amine catalyst is one or a combination of Air Chemical Polycat 8 and Air Chemical Polycat 46; The metal catalyst is one or both of Air Chemical Dabco K-15 and Air Chemical Polycat 46; The polysiloxane foam stabilizer is polyether modified silicone oil; The physical blowing agent is a fluorodichloroethane HCFC141b; The polyisocyanate is a polymethylene polyphenyl polyisocyanate with a mass percentage of NCO groups of 30-32 wt%. 3. The halogen-free highly flame-retardant polyisocyanurate foam according to claim 1, characterized in that: The hypophosphite flame retardant is selected from melamine hypophosphite, aluminum hypophosphite, calcium hypophosphite, cerium hypophosphite, zinc hypophosphite or lanthanum hypophosphite; The ammonium polyphosphate flame retardant is crystalline type II high molecular weight ammonium polyphosphate or microcapsule ammonium polyphosphate with a degree of polymerization n>1000; The organic phosphorus-containing flame retardant is resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), dimethyl methyl phosphonate, diethyl ethyl phosphonate, One or a mixture of trimethyl phosphate and triethyl phosphate. 4. A preparation method of a halogen-free highly flame-retardant polyisocyanurate foam, characterized in that: a. Weigh polyester polyol, amine catalyst, metal catalyst, water, polysiloxane foam stabilizer, physical blowing agent, polyisocyanate, hypophosphite, ammonium polyphosphate and organic phosphorus flame retardant constitute a raw material group; Among them: the mass ratio of polyester polyol, amine catalyst, metal catalyst, water, polysiloxane foam stabilizer, physical blowing agent, and polyisocyanate is 100:1-5:0.1-1:0.5-1.5 :1-3:10-50:250-350; The mass of hypophosphite is 5-15% of the total mass of the raw material group; the mass of ammonium polyphosphate is 0-10% of the total mass of the raw material group; the mass of the organic phosphorus-containing flame retardant is 0-10% of the total mass of the raw material group , and the mass of ammonium polyphosphate and organic phosphorus-containing flame retardant is not 0; b. Mix polyester polyol, amine catalyst, metal catalyst, water, polysiloxane foam stabilizer, physical blowing agent and organic phosphorus-containing flame retardant, and stir evenly to obtain mixture A; c. Mix hypophosphite, ammonium polyphosphate and polyisocyanate, and mechanically stir evenly to obtain mixture B; d. Add the mixture A obtained in step b to the mixture B obtained in step c, stir evenly and pour it into a mold for foaming. After the foam is initiated, take out the foam and place it in a 70-degree oven to mature for 24 hours, that is A halogen-free highly flame-retardant polyisocyanurate foam was obtained. 5. preparation method according to claim 4, is characterized in that: The polyester polyol is a phthalic anhydride polyester polyol with a hydroxyl value of 250-350 mgKOH/g; The amine catalyst is one or a combination of Air Chemical Polycat 8 and Air Chemical Polycat 46; The metal catalyst is one or both of Air Chemical Dabco K-15 and Air Chemical Polycat 46; The polysiloxane foam stabilizer is polyether modified silicone oil; The physical blowing agent is a fluorodichloroethane HCFC141b; The polyisocyanate is a polymethylene polyphenyl polyisocyanate with a mass percentage of NCO groups of 30 to 32 wt %; The hypophosphite is selected from melamine hypophosphite, aluminum hypophosphite, calcium hypophosphite, cerium hypophosphite, zinc hypophosphite or lanthanum hypophosphite; The ammonium polyphosphate is crystalline type II high molecular weight ammonium polyphosphate or microcapsule ammonium polyphosphate with a degree of polymerization n>1000; The organic phosphorus-containing flame retardant is resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), dimethyl methyl phosphonate, diethyl ethyl phosphonate, One or a mixture of trimethyl phosphate and triethyl phosphate.