CN111057202A - Low-odor benzene-based metal phosphonate-containing flame-retardant polyurethane foam material, and preparation method and application thereof - Google Patents

Abstract

The invention discloses a low-odor benzene-based metal phosphonate flame-retardant polyurethane foam material, a preparation method and application thereof, and belongs to the field of preparation of polyurethane foam materials. Comprises the following components: comprises polyether polyol, a catalyst, a foaming agent, a foam stabilizer, a porous material, aryl phosphate and phenylphosphonic acid metal salt; and (B) component: polyphenyl polymethylene polyisocyanates. According to the invention, the polyether polyol and the phenylphosphonic acid metal salt are compounded to form the flame-retardant polyurethane foam, and the phenylphosphonic acid metal salt has better compatibility with polyurethane resin, so that the flame-retardant polyurethane foam has better dispersibility in a flame-retardant polyurethane foam system; and through adding porous adsorption material, used for reducing the smell of the fire-retardant polyurethane foam, solved the big technical problem of polyurethane foam smell in the prior art.

Description

Low-odor benzene-based metal phosphonate-containing flame-retardant polyurethane foam material, and preparation method and application thereof

Technical Field

The invention belongs to the field of preparation of polyurethane foam materials, and particularly relates to a low-odor benzene-based metal phosphonate-containing flame-retardant polyurethane foam material, and a preparation method and application thereof.

Background

Polyurethane (PU) foam has the advantages of excellent thermal insulation, good mechanical properties, excellent weatherability, easy molding processability, etc., and is widely used in the fields of buildings, traffic, household appliances, chemical enterprises, etc. However, PU foam is a very flammable material, and fire accidents caused by the ignition thereof frequently occur, resulting in significant casualties and property damage. Since halogen-containing flame retardants generate a large amount of smoke and toxic and harmful gases during combustion, halogen-free flame retardants are generally added during the preparation of polyurethane foams. According to the patent [201310274749.0; 201710995758.7; 201811060492.8, etc. ] it is reported that dimethyl methyl phosphonate (DMMP) is one of the common halogen-free flame retardants for polyurethane foam because of high phosphorus content and good manufacturability. However, DMMP has a low boiling point (about 180 ℃) and is highly volatile, and is one of the main sources of odor generated by polyurethane foams.

Disclosure of Invention

The invention provides a low-odor benzene-based metal phosphonate flame-retardant polyurethane foam material, a preparation method and application thereof, aiming at solving the technical problems in the background technology.

The invention is realized by the following technical scheme: a low odor, metal phenylphosphonate-containing flame retardant polyurethane foam comprising:

and (2) component A: comprises polyether polyol, a catalyst, a foaming agent, a foam stabilizer, a porous material, aryl phosphate and phenylphosphonic acid metal salt;

and (B) component: polyphenyl polymethylene polyisocyanates.

In a further embodiment, the component a comprises the following materials in parts by mass: 70-110 parts of polyether polyol, 2-6 parts of catalyst, 1-5 parts of foaming agent, 1.5-4 parts of foam stabilizer, 8-24 parts of porous material, 10-25 parts of aryl phosphate and 8-24 parts of metal phenylphosphonate;

and 150 parts of polyphenyl polymethylene polyisocyanate in the component B.

In a further embodiment, the catalyst comprises: one or more of triethanolamine, triethylene diamine and dibutyltin dilaurate.

In a further embodiment, the foaming agent is water and the foam stabilizer is a water-soluble silicone oil.

In a further embodiment, the porous material is a combination of one or more of expanded vermiculite, expanded perlite, molecular sieve, porous silica.

In further embodiments, the aryl phosphate ester comprises: one or two of bisphenol A-bis and resorcinol.

In a further embodiment, the metal phenylphosphonate comprises: magnesium salt, calcium salt, zinc salt, zirconium salt, and aluminum salt.

In a further embodiment, the method specifically comprises the following steps:

step one, polyether polyol, aryl phosphate, phenylphosphonate metal salt and a porous material are uniformly mixed in a stirring device;

step two, continuously adding a catalyst, a foaming agent and a foam stabilizer into a stirring device, and uniformly mixing to obtain a component A;

step three, adding a component B into the component A: polyphenyl polymethylene polyisocyanate, and stirring;

pouring the mixture of the component A and the component B into a mould to foam at normal temperature and normal pressure after the mixture of the component A and the component B is uniformly mixed;

and step five, after foaming and forming, taking out the formed foam, and putting the formed foam in an oven at the temperature of 50-80 ℃ for curing for 20-26 hours to obtain the halogen-free flame-retardant rigid polyurethane foam.

The application of the low-odor benzene-based metal phosphonate flame-retardant polyurethane foam material in buildings, transportation, household appliances and refrigeration houses.

The invention has the beneficial effects that: according to the invention, aryl phosphate with a boiling point of more than 500 ℃ is adopted to replace low-boiling DMMP (dimethyl methylphosphonate) so as to increase the flame retardant property of the prepared polyurethane foam material and solve the technical problems of large volatilization and heavy smell of DMMP;

the polyether polyol and the phenylphosphonic acid metal salt are compounded into the flame-retardant polyurethane foam, and the compounded flame-retardant polyurethane foam has better dispersibility due to the stable cluster compound formed by the phenylphosphonic acid metal salt;

and through adding porous adsorption material, used for reducing the smell of the fire-retardant polyurethane foam, solved the big technical problem of polyurethane foam smell in the prior art.

Detailed Description

The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.

Example 1

Firstly, uniformly mixing 90 parts of polyether polyol, 15 parts of RDP, 16 parts of metal phenylphosphonate and 16 parts of expandable vermiculite, then adding 4 parts of diethanolamine catalyst, 3 parts of water and 2.5 parts of silicone oil foam stabilizer, uniformly mixing, then rapidly adding 130 parts of polymethylene polyphenyl polyisocyanate, uniformly stirring at a high speed, pouring into a mould for foaming, after foam molding, taking out the foam, and placing the foam in a 60 ℃ drying oven for curing for 24 hours to obtain the halogen-free flame-retardant rigid polyurethane foam.

Example 2

Firstly, uniformly mixing 110 parts of polyether polyol, 15 parts of RDP, 16 parts of magnesium phenylphosphonate and 24 parts of expandable vermiculite, then adding 6 parts of diethanolamine catalyst, 4 parts of water and 3 parts of silicone oil foam stabilizer, uniformly mixing, then rapidly adding 130 parts of polymethylene polyphenyl polyisocyanate, uniformly stirring at a high speed, pouring into a mould for foaming, after foam molding, taking out the foam, and placing the foam in a 60 ℃ drying oven for curing for 24 hours to obtain the halogen-free flame-retardant rigid polyurethane foam.

Example 3

Firstly, uniformly mixing 70 parts of polyether polyol, 20 parts of BDP, 24 parts of aluminum phenylphosphinate and 8 parts of expandable vermiculite, then adding 6 parts of triethanolamine catalyst, 1 part of water and 2 parts of silicone oil foam stabilizer, uniformly mixing, then rapidly adding 120 parts of polymethylene polyphenyl polyisocyanate, uniformly stirring at a high speed, pouring into a mould for foaming, after foam molding, taking out the foam, and placing the foam in an oven at 60 ℃ for curing for 24 hours to obtain the halogen-free flame-retardant rigid polyurethane foam.

Example 4

Firstly, uniformly mixing 90 parts of polyether polyol, 15 parts of BDP, 16 parts of copper phenylphosphonate and 8 parts of expanded perlite, then adding 6 parts of triethanolamine catalyst, 1 part of water and 1.5 parts of silicone oil foam stabilizer, uniformly mixing, then rapidly adding 150 parts of polymethylene polyphenyl polyisocyanate, uniformly stirring at a high speed, pouring into a mould for foaming, after foam molding, taking out the foam, and placing the foam in an oven at 60 ℃ for curing for 24 hours to obtain the halogen-free flame-retardant rigid polyurethane foam.

Example 5

Firstly, uniformly mixing 90 parts of polyether polyol, 20 parts of RDP, 16 parts of calcium phenylphosphonate and 16 parts of expandable vermiculite, then adding 6 parts of triethanolamine catalyst, 5 parts of water and 4 parts of silicone oil foam stabilizer, uniformly mixing, then rapidly adding 135 parts of polymethylene polyphenyl polyisocyanate, uniformly stirring at a high speed, pouring into a mould for foaming, after foam molding, taking out the foam, and placing the foam in an oven at 60 ℃ for curing for 24 hours to obtain the halogen-free flame-retardant rigid polyurethane foam.

Example 6

Firstly, uniformly mixing 110 parts of polyether polyol, 10 parts of RDP, 20 parts of zinc phenylphosphonate and 8 parts of expandable vermiculite, then adding 2 parts of triethanolamine catalyst, 4 parts of water and 4 parts of silicone oil foam stabilizer, uniformly mixing, then rapidly adding 150 parts of polymethylene polyphenyl polyisocyanate, uniformly stirring at a high speed, pouring into a mould for foaming, after foam molding, taking out the foam, and placing the foam in an oven at 60 ℃ for curing for 24 hours to obtain the halogen-free flame-retardant rigid polyurethane foam.

Example 7

Firstly, uniformly mixing 90 parts of polyether polyol, 20 parts of RDP, 24 parts of phenyl copper phosphonate and 8 parts of expandable vermiculite, then adding 6 parts of triethanolamine catalyst, 1 part of water and 4 parts of silicone oil foam stabilizer, uniformly mixing, then rapidly adding 135 parts of polymethylene polyphenyl polyisocyanate, uniformly stirring at a high speed, pouring into a mould for foaming, after foam molding, taking out the foam, and placing the foam in an oven at 60 ℃ for curing for 24 hours to obtain the halogen-free flame-retardant rigid polyurethane foam.

Example 8

Firstly, uniformly mixing 90 parts of polyether polyol, 25 parts of RDP, 20 parts of aluminum phenylphosphinate and 24 parts of molecular sieve, then adding 4 parts of diethylenetriamine catalyst, 3 parts of water and 4 parts of silicone oil foam stabilizer, uniformly mixing, then rapidly adding 150 parts of polymethylene polyphenyl polyisocyanate, uniformly stirring at a high speed, pouring into a mould for foaming, after foam molding, taking out the foam, and placing the foam in an oven at 60 ℃ for curing for 24 hours to obtain the halogen-free flame-retardant rigid polyurethane foam.

Control sample

Firstly, uniformly mixing 90 parts of polyether polyol, 4 parts of triethanolamine catalyst, 3 parts of water and 2.5 parts of silicone oil foam stabilizer, then adding 10 parts of DMMP flame retardant, uniformly mixing, then rapidly adding 140 parts of polymethylene polyphenyl polyisocyanate, stirring uniformly at a high speed, pouring into a mold for foaming, after foam molding, taking out the foam, and placing the foam in an oven at 60 ℃ for curing for 24 hours to obtain the halogen-free flame-retardant rigid polyurethane foam.

The following methods were used for evaluation of the odor of the flame-retardant polyurethane foam:

taking 5 parts of samples with the size of 50 mm multiplied by 20 mm, respectively putting the samples into a clean and tasteless 1L glass bottle which is well treated in advance, covering a bottle cap and sealing the bottle, putting the bottle into an oven with the temperature of (80 +/-2) DEG C for 2 hours, taking out the bottle and cooling the bottle to the temperature of (60 +/-5) DEG C, and carrying out detection (taking the sample and putting the sample into the room temperature for about 3 minutes). Evaluation was performed according to the severity of the odor, and evaluation criteria were classified into 5 grades: grade 1, no peculiar smell; grade 2, slightly peculiar smell; grade 3, obvious odor but no pungent taste; grade 4, obvious peculiar smell and pungent smell; grade 5, pungent odor, intolerable.

TABLE 1 Properties of examples 1-8 and control foams

Numbering	Odor grade	UL-94 vertical burn rating
			Example 1	2	V-0
Example 2	2	V-0
			Example 3	2	V-0
Example 4	2	V-0
			Example 5	2	V-0
Example 6	2	V-0
			Example 7	2	V-0
Example 8	2	V-0
			Control sample	5	V-1

According to the data in the table 1, the odor of the flame-retardant polyurethane foam prepared by the invention is greatly reduced from that of the flame-retardant polyurethane foam in the prior art, and the flame-retardant polyurethane foam is only slightly peculiar, so that the application range is enlarged; and from the perspective of flame retardant property, the flame retardant property of the flame retardant polyurethane foam prepared by the invention is improved compared with the flame retardant property of the existing flame retardant polyurethane foam, and the phenyl phosphonic acid metal salt is a filler type flame retardant, so that the flame retardant effect is good.

Claims (9)

1. A low odor, metal phenylphosphonate-containing flame retardant polyurethane foam comprising:

and (2) component A: comprises polyether polyol, a catalyst, a foaming agent, a foam stabilizer, a porous material, aryl phosphate and phenylphosphonic acid metal salt;

and (B) component: polyphenyl polymethylene polyisocyanates.

2. The low-odor metal phenylphosphonate-containing flame-retardant polyurethane foam material as claimed in claim 1,

the component A comprises the following materials in parts by mass: 70-110 parts of polyether polyol, 2-6 parts of catalyst, 1-5 parts of foaming agent, 1.5-4 parts of foam stabilizer, 8-24 parts of porous material, 10-25 parts of aryl phosphate and 8-24 parts of metal phenylphosphonate;

and 150 parts of polyphenyl polymethylene polyisocyanate in the component B.

3. The low odor metal phenylphosphonate-containing flame retardant polyurethane foam of claim 1, wherein the catalyst comprises: one or more of triethanolamine, triethylene diamine and dibutyltin dilaurate.

4. The low-odor metal phenylphosphonate-containing flame-retardant polyurethane foam material as claimed in claim 1, wherein the foaming agent is water, and the foam stabilizer is water-soluble silicone oil.

5. The low-odor metal phenylphosphonate-containing flame retardant polyurethane foam material as claimed in claim 1, wherein the porous material is one or more of expanded vermiculite, expanded perlite, molecular sieve, porous silica.

6. The low odor metal phenylphosphonate-containing flame retardant polyurethane foam of claim 1, wherein the aryl phosphate comprises: one or two of bisphenol A-bis and resorcinol.

7. The low odor metal phenylphosphonate-containing flame retardant polyurethane foam of claim 1, wherein said metal phenylphosphonate comprises: magnesium salt, calcium salt, zinc salt, zirconium salt, and aluminum salt.

8. The preparation method of the low-odor benzene-based metal phosphonate flame-retardant polyurethane foam material is characterized by comprising the following steps:

step one, polyether polyol, aryl phosphate, phenylphosphonate metal salt and a porous material are uniformly mixed in a stirring device;

step two, continuously adding a catalyst, a foaming agent and a foam stabilizer into a stirring device, and uniformly mixing to obtain a component A;

step three, adding a component B into the component A: polyphenyl polymethylene polyisocyanate, and stirring;

pouring the mixture of the component A and the component B into a mould to foam at normal temperature and normal pressure after the mixture of the component A and the component B is uniformly mixed;

and step five, after foaming and forming, taking out the formed foam, and putting the formed foam in an oven at the temperature of 50-80 ℃ for curing for 20-26 hours to obtain the halogen-free flame-retardant rigid polyurethane foam.

9. The use of the low-odor phenylphosphonic acid metal salt-containing flame-retardant polyurethane foam material as defined in claim 1 in buildings, transportation, household appliances and cold storage.