CN102585141B - Flame-retardant polyurethane foam and preparation method thereof - Google Patents
Flame-retardant polyurethane foam and preparation method thereof Download PDFInfo
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Abstract
The invention discloses flame-retardant polyurethane foam and a preparation method thereof. The method comprises the following steps of: (1) in the presence of an acid catalyst, undergoing a first contact reaction on a straw lignin material and polylol to obtain a mixed liquid containing the straw lignin material; (2) undergoing a second contact reaction on phosphoric acid and pentaerythritol at the temperature of 100-180 DEG C for 0.5-5 hours, adding polyether polyol, ammonium polyphosphate and melamine into a product obtained through the second contact reaction, and undergoing a third contact reaction at the temperature of 100-180 DEG C for 0.5-4 hours to obtain a flame retardant; and (3) uniformly mixing the mixed liquid obtained in the step (1) and the flame retardant, polyether polyol, an amine catalyst and the foaming agent obtained in the step (2), adding isocyanate in the ratio of 1-1.4 for undergoing a fourth contact reaction, and curing a product in the fourth contact region. Biomass-based flame-retardant polyurethane foam prepared according to the method disclosed by the invention has high flame retardance.
Description
Technical field
The present invention relates to a kind of preparation method of resistance combustion polyurethane foam, and by the resistance combustion polyurethane foam of this method preparation.
Background technology
Along with people are constantly deep to the understanding of ecocrisis and crisis of resource, the exploitation of natural polymer novel materials such as xylogen, starch comes into one's own day by day.Xylogen and starch belong to natural high moleculer eompound, are the huge and reproducible organic resources of reserves, extensively are present in the plant materials.Urethane is because its cheap, superior performance has become one of the fastest kind of modern polymer industrial development.Because xylogen, starch have multiple functional groups such as hydroxyl, through substituting petroleum base chemical (as the petroleum base polyvalent alcohol) after the exploitation, become the important source of organic compound, be used for macromolecular materials such as synthesis of polyurethane.
Disclose among the CN1543478A and utilized the xylogen method for producing polyurethanes, this method comprises makes many alcoholic solutions and the polyisocyanates generation polycondensation that contains lignosulfonic acid or its part neutralized salt with dissolved state, wherein, the amount of this lignosulfonic acid or its part neutralized salt accounts for 1-40% in total urethane.Yet, do not add fire retardant in this method, make that the flame retardant properties of urethane prepared by this method is relatively poor.Can be used as the additive that fire retardant adds though disclose some in the prior art in preparation urethane process, for example, halogen-containing fire retardant and phosphorated fire retardant, described halogen-containing fire retardant has pentabromodiphenyl oxide and dibromo phenyl glycidyl ether, it is base (as Exolit AP) that described phosphorated fire retardant mainly contains with the ammonium polyphosphate, be base (as Exolit OP) with the organo phosphorous compounds or be the phosphonium flame retardant of base (as Exolit RP) etc. with red phosphorus, but, adopt urethane toxicity when burning of halogen-containing fire retardant preparation bigger, the reactive behavior of the urethane of employing phosphorated fire retardant preparation is lower, can not with the urethane polymerization reaction take place, thereby cause the flame retardant properties of the urethane for preparing thus relatively poor.
Summary of the invention
An object of the present invention is in order to overcome the above-mentioned defective of prior biological matter urethane, a kind of preparation method of new resistance combustion polyurethane foam is provided.
Another object of the present invention provides the resistance combustion polyurethane foam by described method preparation.
The invention provides a kind of preparation method of resistance combustion polyurethane foam, this method may further comprise the steps:
(1) in the presence of an acidic catalyst, straw lignin material and polyvalent alcohol are carried out first contact reacts, obtain containing the mixing liquid of straw lignin material;
(2) under 100-180 ℃, phosphoric acid and tetramethylolmethane were carried out the second contact reacts 0.5-5 hour, in the product that this second contact reacts obtains, add polyether glycol, ammonium polyphosphate and trimeric cyanamide, and under 100-180 ℃, carried out the 3rd contact reacts 0.5-4 hour, obtain fire retardant;
(3) with the described fire retardant, polyether glycol, amines catalyst and the whipping agent uniform mixing that obtain in the described mixing liquid that obtains in the step (1), the step (2), be that 1-1.4 adding isocyanic ester carries out the 4th contact reacts by isocyanate index then, and the product that the 4th contact reacts is obtained is cured.
The present invention also provides a kind of resistance combustion polyurethane foam, and this resistance combustion polyurethane foam is made by aforesaid method.
In described method provided by the invention, in the step (2) fire retardant of preparation can with the urethane polymerization reaction take place, and not halogen-containing, make the resistance combustion polyurethane foam of final preparation have stable flame retardant properties, and toxicity is lower when burning; In addition, according in the process of preparation resistance combustion polyurethane foam of the present invention not needs use volatile solvent, thereby can not pollute environment.
Embodiment
The preparation method of described resistance combustion polyurethane foam provided by the invention may further comprise the steps:
(1) in the presence of an acidic catalyst, straw lignin material and polyvalent alcohol are carried out first contact reacts, obtain containing the mixing liquid of straw lignin material;
(2) under 100-180 ℃, phosphoric acid and tetramethylolmethane were carried out the second contact reacts 0.5-5 hour, in the product that this second contact reacts obtains, add polyether glycol, ammonium polyphosphate and trimeric cyanamide, and under 100-180 ℃, carried out the 3rd contact reacts 0.5-4 hour, obtain fire retardant;
(3) with the described fire retardant, polyether glycol, amines catalyst and the whipping agent uniform mixing that obtain in the described mixing liquid that obtains in the step (1), the step (2), be that 1-1.4 adding isocyanic ester carries out the 4th contact reacts by isocyanate index then, and the product that the 4th contact reacts is obtained is cured.
In the present invention, term " isocyanate index " refers to the ratio of isocyanurate equivalent number and polyvalent alcohol equivalents, the excessive degree of isocyanic ester in the expression polyurethane formulations, described isocyanurate equivalent number is meant the mole number of the isocyano in the isocyanic ester, and described polyvalent alcohol equivalents is meant the mole number of the alcoholic extract hydroxyl group of polyvalent alcohol.
According to described method provided by the invention, in step (1), described first contact reacts is for described straw lignin is carried out modification, to improve its reactive behavior.The described first catalytic reaction conditions can comprise: temperature of reaction is 100-135 ℃, is preferably 120-135 ℃; Reaction times is 1-4 hour, is preferably 1-2 hour.
According to described method provided by the invention, in step (1), with respect to the straw lignin material of 100 weight parts, the add-on of described polyvalent alcohol can be the 90-200 weight part, is preferably the 120-160 weight part; The add-on of described an acidic catalyst can be the 0.1-3 weight part, is preferably the 0.5-2 weight part.
In the present invention, described straw lignin material can be the stalk of various conventional plants, for example can be the stalk of grass, is preferably wheat stalk and/or maize straw.There is no particular limitation for the particle size of described straw lignin material, and under the preferable case, the particle size of described straw lignin material is the 10-200 order.
In the present invention, described polyvalent alcohol can be the polyvalent alcohol of various routines, can be macromolecular polyol, also can be the small molecules polyvalent alcohol, as long as contain at least 2 hydroxyls simultaneously in a molecule.Under the preferable case, described polyvalent alcohol is one or more in ethylene glycol, polyoxyethylene glycol and the glycerine, and the weight-average molecular weight of described polyoxyethylene glycol can be 200-5000, is preferably 400-1000; Under the preferred situation, described polyvalent alcohol is the mixture of polyoxyethylene glycol and glycerine, under this preferable case, glycerine and polyoxyethylene glycol acting in conjunction can suppress the condensation reaction of xylogen, thereby can further improve the reactive behavior of the lignin modification thing of final acquisition.
According to described method provided by the invention, in step (1), when described polyvalent alcohol was the mixture of polyoxyethylene glycol and glycerine, the mixed weight ratio of polyoxyethylene glycol and glycerine was preferably 1-15: 1, and 1.5-10 more preferably: 1.Further under the preferable case, with respect to the straw lignin material of 100 weight parts, the add-on of described polyoxyethylene glycol is preferably the 80-150 weight part, and the add-on of described glycerine is preferably the 10-50 weight part.
In the present invention, described an acidic catalyst can be in phosphoric acid, hydrochloric acid, sulfuric acid, formic acid, acetate, oxalic acid, propanedioic acid, Succinic Acid, Phenylsulfonic acid and the phenylformic acid one or more, most preferably is sulfuric acid.
According to described method provided by the invention, in step (2), make tetramethylolmethane and phosphoric acid generation condensation by described second contact reacts, afterwards by described the 3rd contact reacts, to improve the reactive behavior of fire retardant, make the final fire retardant that obtains have stable flame retardant properties.Yet, if phosphoric acid, tetramethylolmethane, polyether glycol, ammonium polyphosphate and trimeric cyanamide directly mixed and react, then tetramethylolmethane and phosphoric acid condensation are insufficient, influence the reactive behavior of fire retardant, thereby make the finally fire-retardant less stable of the fire retardant of acquisition.
According to described method provided by the invention, the described second catalytic condition comprises: temperature of reaction is 100-180 ℃, and the reaction times is 0.5-5 hour.When temperature of reaction is lower than 100 ℃ or reaction times during less than 0.5 hour, tetramethylolmethane and phosphoric acid can not fully react, thereby can produce adverse influence to the flame retardant properties of the fire retardant of final preparation; And should be with 180 ℃ or reaction times during greater than 5 hours when temperature of reaction, the side reaction that occurs may take place between tetramethylolmethane and the phosphoric acid not wish.In the preferred case, the described second catalytic condition comprises: temperature of reaction is 120-160 ℃, and the reaction times is 1-2 hour.
According to described method provided by the invention, the described the 3rd catalytic condition comprises: temperature of reaction is 100-180 ℃, and the reaction times is 0.5-4 hour.This temperature of reaction is higher than the side reaction that 180 ℃ of then easy generations are not wished to occur, and this temperature of reaction is lower than 100 ℃ and then reacts and can not fully take place.In the preferred case, the described the 3rd catalytic condition comprises: 120-160 ℃, the reaction times is 0.5-2 hour.
According to described method provided by the invention, the described second catalytic condition and the described the 3rd catalytic condition can be identical or different, and preferably the two is identical.
According to described method provided by the invention, in step (2), with respect to the tetramethylolmethane of 100 weight parts, the add-on of described phosphoric acid can be the 75-125 weight part, is preferably the 80-110 weight part; The add-on of described polyether glycol can be the 125-225 weight part, is preferably the 150-210 weight part; The add-on of described ammonium polyphosphate can be the 125-200 weight part, is preferably the 140-185 weight part; The add-on of described trimeric cyanamide can be the 100-200 weight part, is preferably the 120-180 weight part.Described polyether glycol can be the polyether glycol of commercially available various routines, and its weight-average molecular weight is preferably 200-5000, and more preferably 400-1000 for example can be polyether glycol 4110 and/or polyether glycol 403.The polymerization degree of described ammonium polyphosphate can be 50-2000, is preferably 100-1500.
According to described method provided by the invention, in step (3), the described the 4th catalytic reaction conditions can comprise: temperature of reaction is 15-30 ℃, is preferably 15-20 ℃; Reaction times is 0.5-5min, is preferably 1-2min.
According to described method provided by the invention, in step (3), the condition that the product that described the 4th contact reacts is obtained is cured can comprise: the solidified temperature is 60-120 ℃, is preferably 60-80 ℃; The solidified time is 2-24 hour, is preferably 2-10 hour.Described curing can adopt conventional curing to implement, for example baking oven for drying solidification.
According to described method provided by the invention, the add-on of fire retardant, polyether glycol, amines catalyst and the whipping agent that obtains in the described mixing liquid that obtains in the step (1), the step (2) can change separately in the larger context.Under the preferable case, the described mixing liquid that obtains in the step (1) with respect to 100 weight parts, the add-on of described fire retardant is the 20-100 weight part, the add-on of described polyether glycol is the 50-300 weight part, the add-on of described amines catalyst is the 1-10 weight part, and the add-on of described whipping agent is the 10-100 weight part.Mixing liquid, fire retardant, polyether glycol, amines catalyst and the whipping agent that obtains in step (1) all adds fashionable in above-mentioned numerical range, and the resistance combustion polyurethane foam of final preparation has flame retardant properties preferably.Further under the preferable case, the described mixing liquid that obtains in the step (1) with respect to 100 weight parts, the add-on of described fire retardant is the 30-70 weight part, the add-on of described polyether glycol is the 100-200 weight part, the add-on of described amines catalyst is the 1.5-8 weight part, and the add-on of described whipping agent is the 20-50 weight part.Described polyether glycol can be the polyether glycol of commercially available various routines, and its weight-average molecular weight is preferably 200-5000, and more preferably 400-1000 for example can be polyether glycol 4110 and/or polyether glycol 403.
Described amines catalyst can be in triethylene diamine, triethylamine, trolamine and the dimethylcyclohexylamine one or more, most preferably is triethylene diamine.
Described whipping agent can be the whipping agent of various routines, for example can be a fluorine ethylene dichloride, 1,1,1,3, the 3-pentafluoropropane, 1,1,1,3, the 3-3-pentafluorobutane, N, N-dinitroso five methyne tetramines, Cellmic C 121, Diisopropyl azodicarboxylate, diisopropyl azodiformate, diethyl azodiformate, azoformic acid barium, 4, the 4-disulfonyl hydrazide diphenyl ether, p-toluene sulfonyl hydrazide, 1, the 3-benzene disulfohydrazide, 1, the 4-benzene disulfohydrazide, normal butane, Skellysolve A, normal hexane, normal heptane, sherwood oil, trichlorofluoromethane, dichlorofluoromethane, in Refrigerant 12 and the dichloro tetrafluoro ethane one or more.Under the preferable case, described whipping agent is the lower unreactive hydrocarbons compounds of boiling point, as a fluorine ethylene dichloride, 1,1,1,3, and 3-pentafluoropropane and 1,1,1,3, one or more in the 3-3-pentafluorobutane most preferably are a fluorine ethylene dichloride.
Described isocyanic ester is preferably the isocyanic ester (also being vulcabond or polyisocyanates) with two above isocyanos, and described isocyanic ester with two above isocyanos for example can be in tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, poly methylene poly phenyl poly isocyanate and the diphenylmethanediisocyanate one or more.
According to described method provided by the invention, for the mechanical property and the flame retardant properties of the resistance combustion polyurethane foam that improves final preparation, the preparation method of described resistance combustion polyurethane foam can also be included in and add suds-stabilizing agent in the step (3).The described mixing liquid that obtains in the step (1) with respect to 100 weight parts, the add-on of described suds-stabilizing agent can be the 1-10 weight part, is preferably the 1.5-8 weight part.In the present invention, described suds-stabilizing agent is preferably dimethyl siloxane and/or silicone oil.
The present invention also provides the resistance combustion polyurethane foam by method for preparing.
The present invention is further detailed explanation by the following examples.
Embodiment 1
Present embodiment is used to illustrate described resistance combustion polyurethane foam provided by the invention and preparation method thereof.
(1) contains the preparation of the mixing liquid of straw lignin
The maize straw (particle size is the 80-120 order) of 100 weight parts, the polyoxyethylene glycol (PEG400) of 110 weight parts, the glycerine of 30 weight parts and the sulfuric acid (98% the vitriol oil) of 1.5 weight parts are mixed, and under 120 ℃, reacted 2 hours, obtain mixing liquid.
(2) preparation of fire retardant
The tetramethylolmethane of 100 weight parts and the phosphoric acid of 85 weight parts are mixed, and 140 ℃ of following stirring reactions 1 hour, the ammonium polyphosphate of polyether glycol (available from the polyether glycol 4110 of clear month urethane factory of Beijing lark), 160 weight parts that adds 185 weight parts afterwards in reaction product is (available from Beijing Linkage chemical industry company limited, the polymerization degree is 1500) and the trimeric cyanamide of 150 weight parts, and, obtain fire retardant 140 ℃ of following stirring reactions 0.5 hour.
(3) preparation of resistance combustion polyurethane foam
Under agitation, the mixing liquid that obtains in (1) with 100 weight parts, the polyether glycol of 150 weight parts (available from the polyether glycol 4110 of clear month urethane factory of Beijing lark), the triethylene diamine solution of 5 weight parts is (available from clear month urethane factory of Beijing lark, the trade mark is A33), 7.5 the dimethyl siloxane of weight part (available from clear month urethane factory of Beijing lark), the fire retardant uniform mixing of preparation in (2) of one fluorine ethylene dichloride of 50 weight parts (available from clear month urethane factory of Beijing lark) and 60 weight parts, then, to the diphenylmethanediisocyanate that wherein adds 322 weight parts (available from Hangzhou Green's chemical industry trade Co., Ltd), so that isocyanate index is adjusted to 1.2, after stirring, make the mixture that obtains 20 ℃ of following stirring reactions 1.5 minutes, then, in 85 ℃ baking oven, solidified 12 hours, obtain resistance combustion polyurethane foam A1.
Comparative Examples 1
Method according to embodiment 1 prepares resistance combustion polyurethane foam, different is, use the ammonium polyphosphate based flameproofing (available from Guangzhou Feng Tian chemical industry company limited, Exolit AP) of equivalent to replace the fire retardant of preparation in above-mentioned (2), thereby make resistance combustion polyurethane foam D1.
Comparative Examples 2
Method according to embodiment 1 prepares resistance combustion polyurethane foam, different is, in step (2), with the ammonium polyphosphate of the phosphoric acid of the tetramethylolmethane of 100 weight parts, 85 weight parts, the polyether glycol of 185 weight parts (available from the polyether glycol 4110 of clear month urethane factory of Beijing lark), 160 weight parts (available from Beijing Linkage chemical industry company limited, the polymerization degree is 1500) and the trimeric cyanamide of 150 weight parts directly mix, and 140 ℃ of following stirring reactions 1.5 hours, thereby make resistance combustion polyurethane foam D2.
Comparative Examples 3
Method according to embodiment 1 prepares resistance combustion polyurethane foam, and different is, in step (2), tetramethylolmethane and phosphoric acid being reflected under 90 ℃ between the two carried out, thereby makes resistance combustion polyurethane foam D3.
Comparative Examples 4
Method according to embodiment 1 prepares resistance combustion polyurethane foam, and different is, in step (2), tetramethylolmethane and phosphoric acid are reflected under 200 ℃ between the two and carry out, thereby make resistance combustion polyurethane foam D4.
Comparative Examples 5
Method according to embodiment 1 prepares resistance combustion polyurethane foam, and different is that in step (2), being reflected under 90 ℃ after adding polyether glycol, ammonium polyphosphate and the trimeric cyanamide carried out, thereby makes resistance combustion polyurethane foam D5.
Comparative Examples 6
Method according to embodiment 1 prepares resistance combustion polyurethane foam, and different is that in step (2), being reflected under 200 ℃ after adding polyether glycol, ammonium polyphosphate and the trimeric cyanamide carried out, thereby makes resistance combustion polyurethane foam D6.
Embodiment 2
Present embodiment is used to illustrate described resistance combustion polyurethane foam provided by the invention and preparation method thereof.
(1) contains the preparation of the mixing liquid of straw lignin
The wheat stalk (particle size is the 10-50 order) of 100 weight parts, the polyoxyethylene glycol of 80 weight parts, the glycerine of 50 weight parts and the sulfuric acid (98% the vitriol oil) of 0.5 weight part are mixed, and reacted 1.5 hours down, obtain mixing liquid at 135 ℃.
(2) preparation of fire retardant
The tetramethylolmethane of 100 weight parts and the phosphoric acid of 80 weight parts are mixed, and 130 ℃ of following stirring reactions 1.5 hours, the ammonium polyphosphate of polyether glycol (available from the polyether glycol 403 of clear month urethane factory of Beijing lark), 185 weight parts that adds 210 weight parts afterwards in reaction product is (available from Beijing Linkage chemical industry company limited, the polymerization degree is 100) and the trimeric cyanamide of 120 weight parts, and, obtain fire retardant 130 ℃ of following stirring reactions 0.5 hour.
(3) preparation of resistance combustion polyurethane foam
Under agitation, the mixing liquid that obtains in (1) with 100 weight parts, the polyether glycol of 100 weight parts (available from the polyether glycol 403 of clear month urethane factory of Beijing lark), 1.5 the trolamine of weight part (available from Beijing China imperial chemical industry company limited), the dimethyl siloxane of 5 weight parts (available from clear month urethane factory of Beijing lark), 1 of 40 weight parts, 1,1,3, the fire retardant uniform mixing of preparation in (2) of 3-pentafluoropropane (available from clear month urethane factory of Beijing lark) and 70 weight parts, then, to the hexamethylene diisocyanate that wherein adds 302 weight parts (available from Hangzhou Green's chemical industry trade Co., Ltd), so that isocyanate index is adjusted to 1.0, after stirring, make the mixture that obtains 20 ℃ of following stirring reactions 30 seconds, then, in 85 ℃ baking oven, solidified 12 hours, obtain resistance combustion polyurethane foam A2.
Embodiment 3
Present embodiment is used to illustrate described resistance combustion polyurethane foam provided by the invention and preparation method thereof.
(1) contains the preparation of the mixing liquid of straw lignin
The maize straw (particle size is the 100-150 order) of 100 weight parts, the polyoxyethylene glycol of 145 weight parts, the glycerine of 15 weight parts and the sulfuric acid (98% the vitriol oil) of 2 weight parts are mixed, and reacted 1 hour down, obtain mixing liquid at 130 ℃.
(2) preparation of fire retardant
The tetramethylolmethane of 100 weight parts and the phosphoric acid of 110 weight parts are mixed, and 150 ℃ of following stirring reactions 1 hour, the ammonium polyphosphate of polyether glycol (available from the polyether glycol 4110 of clear month urethane factory of Beijing lark), 140 weight parts that adds 150 weight parts afterwards in reaction product is (available from Beijing Linkage chemical industry company limited, the polymerization degree is 1500) and the trimeric cyanamide of 180 weight parts, and, obtain fire retardant 150 ℃ of following stirring reactions 0.5 hour.
(3) preparation of resistance combustion polyurethane foam
Under agitation, the mixing liquid that obtains in (1) with 100 weight parts, the polyether glycol (available from the polyether glycol 403 of clear month urethane factory of Beijing lark) of polyether glycol of 80 weight parts (available from the polyether glycol 4110 of clear month urethane factory of Beijing lark) and 120 weight parts, the triethylene diamine solution of 8 weight parts (available from clear month urethane factory of Beijing lark), 1.5 the silicone oil of weight part (available from clear month urethane factory of Beijing lark), the fire retardant uniform mixing of preparation in (2) of one fluorine ethylene dichloride of 20 weight parts (available from clear month urethane factory of Beijing lark) and 30 weight parts, then, to the tolylene diisocyanate that wherein adds 597 weight parts (available from Hangzhou Green's chemical industry trade Co., Ltd), so that isocyanate index is adjusted to 1.4, after stirring, make the mixture that obtains 20 ℃ of following stirring reactions 3 minutes, then, in 85 ℃ baking oven, solidified 12 hours, obtain resistance combustion polyurethane foam A3.
Test case
(1) flame retardant properties of the resistance combustion polyurethane foam D1-D6 for preparing among resistance combustion polyurethane foam A1-A3 for preparing among the method detection embodiment 1-3 of use taper calorimeter according to ISO 5660:2002 and the Comparative Examples 1-6;
(2) detect the density of the resistance combustion polyurethane foam D1-D6 for preparing among the resistance combustion polyurethane foam A1-A3 for preparing among the embodiment 1-3 and the Comparative Examples 1-6 according to GB/T 6343-1995 " mensuration of porous plastics and rubber apparent (volume) density " method testing method;
(3) detect the compressive strength of the resistance combustion polyurethane foam D1-D6 for preparing among the resistance combustion polyurethane foam A1-A3 for preparing among the embodiment 1-3 and the Comparative Examples 1-6 according to GB8813-2008 " mensuration of rigid foam compression performance " method;
Above-mentioned test result is as shown in table 1 below:
Table 1
As can be seen, the prepared according to the methods of the invention resistance combustion polyurethane foam has good flame retardant property and mechanical property from above-mentioned table 1.And, by embodiment 1 is compared as can be seen with Comparative Examples 1 and 2, owing to do not use the prepared according to the methods of the invention fire retardant in the preparation process of resistance combustion polyurethane foam D1 and D2, thereby cause the flame retardant properties of the final resistance combustion polyurethane foam that obtains relatively poor.
Above embodiment only is used to describe preferred implementation of the present invention; but; the present invention is not limited to the detail in the above-mentioned embodiment; in technical conceive scope of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
Need to prove that in addition each the concrete technical characterictic described in above-mentioned embodiment under reconcilable situation, can make up by any suitable manner.For fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, also can carry out arbitrary combination between the various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. the preparation method of a resistance combustion polyurethane foam, this method may further comprise the steps:
(1) in the presence of an acidic catalyst, straw lignin material and polyvalent alcohol are carried out first contact reacts, obtain containing the mixing liquid of straw lignin material;
(2) under 100-180 ℃, phosphoric acid and tetramethylolmethane were carried out the second contact reacts 0.5-5 hour, in the product that this second contact reacts obtains, add polyether glycol, ammonium polyphosphate and trimeric cyanamide, and under 100-180 ℃, carried out the 3rd contact reacts 0.5-4 hour, obtain fire retardant, wherein, tetramethylolmethane with respect to 100 weight parts, the add-on of described phosphoric acid is the 75-125 weight part, the add-on of described polyether glycol is the 125-225 weight part, the add-on of described ammonium polyphosphate is the 125-200 weight part, and the add-on of described trimeric cyanamide is the 100-200 weight part;
(3) with the described fire retardant, polyether glycol, amines catalyst and the whipping agent uniform mixing that obtain in the described mixing liquid that obtains in the step (1), the step (2), be that 1-1.4 adding isocyanic ester carries out the 4th contact reacts by isocyanate index then, and the product that the 4th contact reacts is obtained is cured.
2. method according to claim 1, wherein, the described first catalytic condition comprises: temperature of reaction is 100-135 ℃, the reaction times is 1-4 hour.
3. method according to claim 1, wherein, in step (1), with respect to the straw lignin material of 100 weight parts, the add-on of described polyvalent alcohol is the 90-200 weight part, the add-on of described an acidic catalyst is the 0.1-3 weight part.
4. according to claim 1 or 3 described methods, wherein, described polyvalent alcohol is at least a in ethylene glycol, polyoxyethylene glycol and the glycerine; Described an acidic catalyst is at least a in phosphoric acid, hydrochloric acid, sulfuric acid, formic acid, acetate, oxalic acid, propanedioic acid, Succinic Acid, Phenylsulfonic acid and the phenylformic acid; The particle size of described straw lignin material is the 10-200 order.
5. according to claim 1 or 3 described methods, wherein, described polyvalent alcohol is the mixture of polyoxyethylene glycol and glycerine.
6. method according to claim 1, wherein, in step (3), the described mixing liquid that obtains in the step (1) with respect to 100 weight parts, the add-on of described fire retardant is the 20-100 weight part, the add-on of described polyether glycol is the 50-300 weight part, and the add-on of described amines catalyst is the 1-10 weight part, and the add-on of described whipping agent is the 10-100 weight part.
7. according to claim 1 or 6 described methods, wherein, described amines catalyst is one or more of triethylene diamine, triethylamine, trolamine and dimethylcyclohexylamine; Described whipping agent is a fluorine ethylene dichloride, 1,1,1,3, the 3-pentafluoropropane, 1,1,1,3, the 3-3-pentafluorobutane, N, N-dinitroso five methyne tetramines, Cellmic C 121, Diisopropyl azodicarboxylate, diisopropyl azodiformate, diethyl azodiformate, azoformic acid barium, 4, the 4-disulfonyl hydrazide diphenyl ether, p-toluene sulfonyl hydrazide, 1, the 3-benzene disulfohydrazide, 1, the 4-benzene disulfohydrazide, normal butane, Skellysolve A, normal hexane, normal heptane, sherwood oil, trichlorofluoromethane, dichlorofluoromethane, in Refrigerant 12 and the dichloro tetrafluoro ethane one or more; Described isocyanic ester is one or more in tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, poly methylene poly phenyl poly isocyanate and the diphenylmethanediisocyanate.
8. method according to claim 1, wherein, the described the 4th catalytic reaction conditions comprises: temperature of reaction is 15-30 ℃, the reaction times is 0.5-5 minute.
9. method according to claim 1, wherein, described solidified condition comprises: the solidified temperature is 60-120 ℃, the solidified time is 2-24 hour.
10. resistance combustion polyurethane foam, this resistance combustion polyurethane foam is made by any described method among the claim 1-9.
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| CN102796318A (en) * | 2012-07-26 | 2012-11-28 | 中国石油大学(北京) | Synthetic method of phosphorus and nitrogen type fire retardant |
| US9346922B2 (en) | 2013-11-26 | 2016-05-24 | International Business Machines Corporation | Flame retardant block copolymers from renewable feeds |
| US9284414B2 (en) | 2013-11-26 | 2016-03-15 | Globalfoundries Inc. | Flame retardant polymers containing renewable content |
| TWI500662B (en) | 2013-12-27 | 2015-09-21 | Ind Tech Res Inst | Bio-polyol composition and bio-polyurethane foam material |
| CN104311816A (en) * | 2014-11-11 | 2015-01-28 | 上海应用技术学院 | Method for preparing polyether glycol with rape stalks as raw materials |
| CN104479531B (en) * | 2014-12-09 | 2016-11-23 | 张和庆 | A kind of solid wood granule plate isophorone diisocyanate fireproof coating and preparation method |
| CN106508898B (en) * | 2015-09-11 | 2020-04-24 | 沈阳化工研究院有限公司 | Biomass-based slow-release pesticide and preparation method thereof |
| CN105694357B (en) * | 2016-01-17 | 2018-01-09 | 浙江省林业科学研究院 | The preparation method of polyether-modified biomass resin foamed rapidly at normal temperature |
| EP3681954A4 (en) | 2017-09-13 | 2021-06-09 | Daren Laboratories & Scientific Consultants Ltd. | Lignin based flame retardant compositions and processes for the preparation thereof |
| CN107805384A (en) * | 2017-11-27 | 2018-03-16 | 倪修俊 | A kind of glass bead polyurethane foam composite of fire-retardant heat insulation and preparation method thereof |
| CN109627452B (en) * | 2018-12-12 | 2021-05-04 | 怀化学院 | Flame retardant for poly (butylene succinate), flame-retardant poly (butylene succinate) material and preparation method thereof |
| CN109627453B (en) * | 2018-12-12 | 2021-05-04 | 怀化学院 | Flame retardant for polylactic acid, flame-retardant polylactic acid material and preparation method thereof |
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