Phosphorus-containing flame retardant with hydroxyl and preparation method and application thereof
阅读说明：本技术 一种带有羟基的含磷阻燃剂及其制备方法和应用 (Phosphorus-containing flame retardant with hydroxyl and preparation method and application thereof ) 是由 潘庆崇 于 2019-08-28 设计创作，主要内容包括：本发明提供了一种带有羟基的含磷阻燃剂及其制备方法和应用。所述含磷阻燃剂具有如式I所示结构。本发明提供的含有羟基的含磷阻燃剂带有羟基官能团,因此可与含羧基、环氧基、异氰酸酯等基团的高分子单体发生反应,在合成包含高分子化合物时,将本发明的带有羟基的含磷阻燃剂作为反应原料加入,阻燃单元将以嵌入、交联等方式接入高分子链段中,从而可以赋予高分子永久性阻燃。(The invention provides a phosphorus-containing flame retardant with hydroxyl and a preparation method and application thereof. The phosphorus-containing flame retardant has a structure shown in a formula I. The phosphorus-containing flame retardant containing hydroxyl provided by the invention has a hydroxyl functional group, so that the phosphorus-containing flame retardant can react with a high polymer monomer containing carboxyl, epoxy, isocyanate and other groups, when a high polymer compound is synthesized, the phosphorus-containing flame retardant containing hydroxyl is used as a reaction raw material, and a flame retardant unit is inserted into a high polymer chain segment in an embedding, crosslinking and other modes, so that the high polymer can be permanently flame-retardant.)
1. A phosphorus-containing flame retardant with hydroxyl groups is characterized by having a structure shown as a formula I:
wherein Z is1、Z2Each independently selected from phosphorus-containing groups;
M1selected from linear alkylene, branched alkylene or arylene;
M2selected from any organic group that satisfies a chemical environment;
Y1、Y2each independently selected from an inert group, a sulfur atom, an oxygen atom, or-H;
X1selected from any organylene group that satisfies a chemical environment;
a. b, c, d, f, g and h are respectively and independently selected from integers of 0-5, a and b are not 0 at the same time, f and g are not 0 at the same time, g and h are not 0 at the same time, and meanwhile, b + c + h is less than or equal to 5 and a + d + g is less than or equal to 5;
e is an integer of 0 to 100.
2. The phosphorus-containing flame retardant having hydroxyl groups as claimed in claim 1, wherein Z is1、Z2Each independently preferablyR1Is any one of saturated or unsaturated alkyl, aryl or heteroaryl, further preferably methyl, ethyl or phenyl;
preferably, a + b.gtoreq.2, more preferably a + b.gtoreq.2.
3. The phosphorus-containing flame retardant having hydroxyl group according to claim 1 or 2, wherein M is1Selected from the group consisting of C1-C30 linear or branched alkylene, C6-C30 arylene, and C5-C7 heteroarylene, more preferably C1-C5 linear alkylene, C3-C5 branched alkylene, or phenyl, still more preferably C1-C3 linear alkylene, C3 branched alkylene, or phenyl.
4. Phosphorus-containing flame retardant having hydroxyl groups according to any of claims 1 to 3, wherein M is2Selected from N, S, C1-C30 straight chain or branched chain alkyl, C6-C30 aryl, C5-C7 heteroaryl, Wherein R is2、R3、R4、R5、R6、R7、R8、R9Each independently of the others is preferably a linear or branched alkylene group having from C1 to C10, L2、Y2、Z2Is connected to R2、R3、R4、R5、R6、R7、R8、R9N, m, i, k are each independently an integer preferably from 0 to 100.
5. The phosphorus-containing flame retardant having hydroxyl groups as claimed in any of claims 1 to 4, wherein Y is1、Y2Each independently is preferably-H or ═ O;
preferably, said X1Selected from N, S, substituted or unsubstituted C1-C30 linear or branched alkylene, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C5-C7 heteroarylene, substituted or unsubstituted C1-C30 alkyleneamine, substituted or unsubstituted C1-C30 alkyleneacyl, substituted or unsubstituted C1-C30 alkyleneester, substituted or unsubstituted C6-C30 alkyleneamine, substituted or unsubstituted C6-C30 aryleneacyl or C6-C30 aryleneester, further preferably substituted or unsubstituted C1-C5 linear or branched alkylene, substituted or unsubstituted C1-C5 alkyleneamine, substituted or unsubstituted C1-C5 alkyleneacyl or substituted or unsubstituted C1-C5 alkyleneester, further preferably-NH-R-, -R '-NH-, -R' -O-, -RV-C (O) -, substituted or unsubstituted C1-C5 linear or branched alkylene, wherein, R, R', R ", RVEach independently is preferably a substituted or unsubstituted C1-C10 straight or branched chain alkylene group.
6. The phosphorus-containing flame retardant having hydroxyl groups according to any one of claims 1 to 5, wherein R is2、R3、R4、R5、R6、R7、R8、R9Independently of one another, they are preferably C1-C6 linear or branched alkylene radicals.
7. Phosphorus-containing flame retardant with hydroxyl groups according to any of claims 1 to 6, characterized in that n, m, i, k are each independently preferably an integer from 0 to 30.
8. Phosphorus-containing flame retardant with hydroxyl groups according to any of claims 1 to 7, characterized in that the phosphorus-containing flame retardant with hydroxyl groups preferably has the structure according to formula II, formula III, formula IV, formula V or formula VI:
wherein M is1Selected from C1-C3 linear alkylene, C3 branched alkylene or phenyl;
M2selected from N, -NH-RTStraight chain or branched chain alkyl of C1-C6,
Wherein R isTIs a linear or branched alkyl group of C1-C6, R2、R3、R4、R5、R6、R7、R8、R9Each independently is a linear or branched alkylene group preferably having C1-C6, and each of n, m, i and k independently is an integer preferably having 0-30;
R1is a firstOr ethyl;
R、R'、R”、RV、RPeach independently a linear or branched alkylene group preferably having C1-C10 which may be substituted or unsubstituted;
Y1、Y2each independently is preferably-H or ═ O;
a. b, g and h are preferably 0, 1 or 2 independently, a and b are not 0 at the same time, a + b is 2, f and g are not 0 at the same time, and g and h are not 0 at the same time;
e is an integer of 0 to 20, and f is 0 or 1.
9. Use of a phosphorus containing flame retardant with hydroxyl groups according to any of claims 1 to 8 for the preparation of polyurethane resins, phenolic resins, polyester resins, alkyd resins or silicone rubber resins.
Technical Field
The invention belongs to the technical field of flame retardants, and relates to a phosphorus-containing flame retardant with hydroxyl groups, and a preparation method and application thereof.
Background
Most of polymer materials are flammable materials, and in order to be safe, polymer products are increasingly required to have flame retardant capability. In order to improve the flame retardant property of the material, the method widely adopted at present is to add flame retardant into various polymer matrixes.
The traditional halogen flame retardant generates more smoke and releases irritant and corrosive gases during combustion, thereby polluting the environment and being harmful to human health; the current flame retardant development field shows the trends of no halogenation, high efficiency, low smoke and no toxicity. The phosphorus-containing flame retardant is one of the phosphorus flame retardants which are rapidly developed in recent years, and is an important halogen-free flame retardant with a wide application prospect. A small amount of the flame retardant is added into the polymer material, so that a good flame retardant effect can be achieved.
Phosphorus-containing flame retardants can be classified into additive and reactive types. The additive flame retardant is directly added into a polymer matrix, so that the material obtains a flame retardant effect, does not chemically react with the base material and other components in the base material, is physically dispersed in the base material to endow the flame retardancy, and the mechanical property of the flame-retardant matrix is often damaged and the quality of the material is influenced due to the large addition amount of the flame retardant. And because part of the added flame retardant is micromolecule flame retardant, micromolecule migration phenomenon can occur along with the prolonging of time, the flame retardant property of the material is reduced, and the water-soluble part of the added flame retardant loses the flame retardant property due to the fact that the added flame retardant is water-soluble and is dissolved in water.
Therefore, the development of a phosphorus-containing flame retardant which can really realize safety, environmental protection and flame retardance is needed to meet the application requirements.
Disclosure of Invention
The invention aims to provide a phosphorus-containing flame retardant with hydroxyl and a preparation method and application thereof. The phosphorus-containing flame retardant containing hydroxyl provided by the invention has a hydroxyl functional group, so that the phosphorus-containing flame retardant can react with a high polymer monomer containing carboxyl, epoxy, isocyanate and other groups, when a high polymer compound is synthesized, the phosphorus-containing flame retardant containing hydroxyl is used as a reaction raw material, and a flame retardant unit is inserted into a high polymer chain segment in an embedding, crosslinking and other modes, so that the high polymer can be permanently flame-retardant.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a phosphorus-containing flame retardant with hydroxyl groups, wherein the phosphorus-containing flame retardant has a structure represented by formula I:
wherein Z is1、Z2Each independently is preferably a phosphorus-containing group.
M1Selected from linear alkylene, branched alkylene or arylene.
M2Selected from any organic group that satisfies the chemical environment.
Y1、Y2Each independently is preferably an inert group, a sulfur atom, an oxygen atom or-H.
X1Selected from any organylene group that satisfies a chemical environment.
a. b, c, d, f, g, h are each independently an integer preferably from 0 to 5, e.g., 1, 2, 3, 4, etc., and a, b are not simultaneously 0, f, g are not simultaneously 0, g, h are not simultaneously 0, while b + c + h ≦ 5 (e.g., b + c + h ≦ 4, b + c + h ≦ 3, b + c + h ≦ 2, etc.) and a + d + g ≦ 5 (e.g., a + d + g ≦ 4, a + d + g ≦ 3, a + d + g ≦ 2, etc.).
e is an integer from 0 to 100, such as 2,5, 10, 20, 30, 40, 50, 60, 70, 80, 90, and the like.
The phosphorus-containing flame retardant with hydroxyl can participate in the reaction for preparing a high polymer base material, such as the reaction with carboxyl to prepare polyester and the like; the phosphorus-containing flame retardant with hydroxyl groups provided by the invention exists in the polymer matrix resin in the form of molecular chain fragments, so that the phenomenon of micromolecule precipitation can be avoided, and the phenomenon that some additive flame retardants lose flame retardance due to water solubility is avoided.
The phosphorus-containing flame retardant with hydroxyl provided by the invention is phenolic hydroxyl when the hydroxyl is connected with an aromatic group, and the hydroxyl also comprises the phenolic hydroxyl.
Preferably, Z1、Z2Each independently preferably R1Is methyl or ethyl.
Preferably, a + b.gtoreq.2, more preferably a + b.gtoreq.2.
Preferably, said M1Selected from the group consisting of C1-C30 linear or branched alkylene, C6-C30 arylene, and C5-C7 heteroarylene, more preferably C1-C5 linear alkylene, C3-C5 branched alkylene, or phenyl, still more preferably C1-C3 linear alkylene, C3 branched alkylene, or phenyl.
The C1-C30 can be C2, C4, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 and the like.
The C6-C30 can be C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 and the like.
The C5-C7 may be C6 or the like.
The C1-C5 linear alkylene group may be methylene, ethylene, propylene, butylene, etc.
The C3-C5 may be C3, C4, C5, etc.
The C1-C3 may be C1, C2, C3, etc.
Preferably, said M2Selected from N, S, C1-C30 straight chain or branched chain alkyl, C6-C30 aryl, C5-C7 heteroaryl,
Wherein R is2、R3、R4、R5、R6、R7、R8、R9Each independently of the others is preferably a linear or branched alkylene group having from C1 to C10, L2、Y2、Z2Is connected to R2、R3、R4、R5、R6、R7、R8、R9N, m, i, k are each independently an integer preferably from 0 to 100, e.g. 2,5, 10, 20, 30, 40, 50, 60, 70, 80, 90 etc.
The C1-C30 can be C2, C4, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 and the like.
The C6-C30 can be C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 and the like.
The C5-C7 may be C6 or the like.
Preferably, Y1、Y2Each independently is preferably-H or ═ O.
Preferably, said X1Selected from N, S, substituted or unsubstituted C1-C30 linear or branched alkylene, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C5-C7 heteroarylene, substituted or unsubstituted C1-C30 alkyleneamine, substituted or unsubstituted C1-C30 alkyleneacyl, substituted or unsubstituted C1-C30 alkyleneester, substituted or unsubstituted C6-C30 alkyleneamine, substituted or unsubstituted C6-C30 aryleneacyl or C6-C30 aryleneester, further preferably substituted or unsubstituted C1-C5 linear or branched alkylene, substituted or unsubstituted C1-C5 alkyleneamine, substituted or unsubstituted C1-C5 alkyleneacyl or substituted or unsubstituted C1-C5 alkyleneester, further preferably-NH-R-, -R '-NH-, -R' -O-, -RV-C (O) -, substituted or unsubstituted C1-C5 linear or branched alkylene, wherein, R, R', R ", RVEach independently is preferably a substituted or unsubstituted C1-C10 straight or branched chain alkylene group.
The term "substituted" as used herein means that any one or more hydrogen atoms on the designated atom is replaced with a substituent selected from the designated group, provided that the designated atom does not exceed a normal valence and that the result of the substitution is a stable compound. When the substituent is an oxo group or a keto group (i.e., ═ O), then 2 hydrogen atoms on the atom are substituted. The ketone substituent is absent on the aromatic ring. By "stable compound" is meant a compound that can be isolated from a reaction mixture sufficiently robustly to an effective purity and formulated to be effective.
The C1-C30 can be C2, C4, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 and the like.
The C6-C30 can be C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 and the like.
The C5-C7 may be C6 or the like.
The C1-C5 may be C1, C2, C3, C4, C5, etc.
The following description is merely an explanation of structures such as alkyleneamino groups, and R does not particularly denote any meaning.
The alkyleneamino group refers to-R-NH-, wherein R is alkylene.
The alkylene acyl refers to-R-C (O) -, wherein R is alkylene.
The alkylene ester group means-R-COO-wherein R represents an alkylene group.
The arylene amine group means-Ar-NH-, wherein Ar represents an arylene group.
The aryleneacyl group means-Ar-C (O) -, wherein Ar represents an arylene group.
The arylene ester group means-Ar-COO-in which Ar represents an arylene group.
Preferably, said R is2、R3、R4、R5、R6、R7、R8、R9Independently of one another, they are preferably C1-C6 linear or branched alkylene radicals.
The C1-C6 may be C2, C3, C4, C5, etc.
Preferably, n, m, i, k are each independently integers preferably from 0 to 30, such as 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, etc.
Preferably, the phosphorus-containing flame retardant with hydroxyl has a structure shown in formula II, formula III, formula IV, formula V or formula VI:
wherein M is1Is selected from C1-C3 linear alkylene, C3 branched alkylene or phenyl.
M2Selected from N, -NH-RTStraight chain or branched chain alkyl of C1-C6,
Wherein R isTIs a linear or branched alkyl group of C1-C6, R2、R3、R4、R5、R6、R7、R8、R9Each independently is preferably a C1-C6 (e.g., C2, C3, C4, C5) straight or branched chain alkylene group, and each of n, m, i, k independently is preferably an integer of 0-30, such as 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, etc.
R1Is methyl or ethyl.
R、R'、R”、RV、RPEach independently is preferably a substituted or unsubstituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.) straight or branched alkylene group.
Y1、Y2Each independently is preferably-H or ═ O.
a. b, g and h are preferably 0, 1 or 2 independently, a and b are not 0 at the same time, a + b is 2, f and g are not 0 at the same time, and g and h are not 0 at the same time.
e is an integer from 0 to 20, e.g., 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 19, etc., and f is 0 or 1.
The invention does not limit the preparation method of the phosphorus-containing flame retardant with hydroxyl, and any preparation method capable of obtaining the compound of the invention can be adopted, and the preparation method is exemplified as follows:
in a second aspect, the present invention provides a method for preparing a phosphorus-containing flame retardant having hydroxyl groups according to the first aspect, the method comprising:
the phosphorus-containing flame retardant with hydroxyl is obtained by the addition reaction of a compound containing a-P-H bond and a compound containing an unsaturated bond and/or a cyclic group.
In a third aspect, the present invention provides a use of the phosphorus-containing flame retardant having hydroxyl groups according to the first aspect for preparing a polyurethane resin, a phenol resin, a polyester resin, a polyamide resin, an alkyd resin or a silicone rubber resin.
The phosphorus-containing flame retardant with hydroxyl provided by the invention can be used as a preparation raw material for preparing polyurethane resin, phenolic resin and silicon rubber, reacts with other components in the raw material, and participates in the reaction process.
Compared with the prior art, the invention has the following beneficial effects:
(1) the phosphorus-containing flame retardant with hydroxyl can participate in the reaction for preparing a high polymer base material, such as the reaction with carboxyl to prepare polyester and the like; the phosphorus-containing flame retardant with hydroxyl groups provided by the invention exists in the polymer matrix resin in the form of molecular chain fragments, so that the phenomenon of micromolecule precipitation can be avoided, and the phenomenon that some additive flame retardants lose flame retardance due to water solubility is avoided.
(2) The phosphorus-containing flame retardant with hydroxyl provided by the invention has good flame retardant performance and mechanical performance, such as polyurethane resin, phenolic resin, polyester resin, polyamide resin, alkyd resin or silicone rubber resin and the like prepared from the phosphorus-containing flame retardant with hydroxyl.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Preparation example 1
A phosphorus-containing flame retardant with hydroxyl groups has the following structure:
the preparation method comprises the following steps:
adding 2mol of dimethyl phosphite, 1mol of pentanedione and 50mL of ethanol into a three-neck flask with a magnetic stirring thermometer, stirring, controlling the temperature below 5 ℃ in an ice-water bath, dropwise adding 2mol of triethylamine, gradually heating and refluxing, continuously reacting for 1h, and carrying out reduced pressure distillation to obtain the reactive flame retardant with the structure.
1H NMR(400MHz,DMSO-d6):δ＝6.60-6.62(s,2H,-OH),3.40-3.45(d,12H,-P-O-CH3),1.7-1.8(s,2H,-CH2),1.3-1.32(s,6H,-CH3).
Preparation example 2
A phosphorus-containing flame retardant with hydroxyl groups has the following structure:
the preparation method comprises the following steps:
adding 2mol of dimethyl phosphite, 1mol of 2, 5-hexanedione and 50mL of ethanol into a three-neck flask with a magnetic stirring thermometer, stirring, controlling the temperature to be below 5 ℃ in an ice-water bath, dropwise adding 2mol of triethylamine, gradually heating and refluxing, continuously reacting for 1h, and carrying out reduced pressure distillation to obtain the reactive flame retardant with the structure.
1H NMR(400MHz,DMSO-d6):δ＝3.40-3.45(d,12H,-P-O-CH3),1.36-1.40(t,4H,-C-C 2H-C 2H-C-),1.20-1.22(s,6H,-CH3).
Preparation example 3
A phosphorus-containing flame retardant with hydroxyl groups has the following structure:
the preparation method comprises the following steps:
adding 2mol of dimethyl phosphite, 1mol of 2, 6-heptanedione and 50mL of ethanol into a three-neck flask with a magnetic stirring thermometer, stirring, controlling the temperature below 5 ℃ in an ice-water bath, dropwise adding 2mol of triethylamine, gradually heating and refluxing, continuously reacting for 1h, and carrying out reduced pressure distillation to obtain the reactive flame retardant with the structure.
1H NMR(400MHz,DMSO-d6):δ＝3.40-3.45(d,12H,-P-O-CH3),1.35-1.40(t,4H,-C 2H-CH2-C 2H-),1.30-1.33(m,2H,-CH2-C 2H-CH2-),1.19-1.21(s,6H,-CH3).
Preparation example 4
A phosphorus-containing flame retardant with hydroxyl groups has the following structure:
the preparation method comprises the following steps:
adding 2mol of dimethyl phosphite, 1mol of 3, 6-octanedione and 50mL of ethanol into a three-neck flask with a magnetic stirring thermometer, stirring, controlling the temperature below 5 ℃ in an ice-water bath, dropwise adding 2mol of triethylamine, gradually heating and refluxing, continuously reacting for 1h, and carrying out reduced pressure distillation to obtain the reactive flame retardant with the structure.
1H NMR(400MHz,DMSO-d6):δ＝3.40-3.45(d,12H,-P-O-CH3),1.36-1.40(m,8H,-C 2H-C-C 2H-C 2H-C-C 2H-),0.98-1.02(t,6H,-CH3).
Preparation example 5
A phosphorus-containing flame retardant with hydroxyl groups has the following structure:
the preparation method comprises the following steps:
adding 2mol of dimethyl phosphite, 1mol of glyoxal and 20mL of ethanol into a three-neck flask with a magnetic stirring thermometer, stirring, controlling the temperature below 5 ℃ in an ice-water bath, dropwise adding 2mol of triethylamine, gradually heating to 50 ℃, continuing to react for 1h, and carrying out reduced pressure distillation to obtain the reactive flame retardant with the structure.
1H NMR(400MHz,DMSO-d6):δ＝6.20-6.22(d,2H,-OH),3.70-3.76(m,2H,-CH-),3.48-3.52(d,12H,-P-O-CH3).
Preparation example 6
A phosphorus-containing flame retardant with hydroxyl groups has the following structure:
the preparation method comprises the following steps:
adding 2mol of dimethyl phosphite, 1mol of malondialdehyde and 20mL of ethanol into a three-neck flask with a magnetic stirring thermometer, stirring, controlling the temperature below 5 ℃ in an ice-water bath, dropwise adding 2mol of triethylamine, gradually heating to 50 ℃, continuing to react for 1h, and carrying out reduced pressure distillation to obtain the reactive flame retardant with the structure.
1H NMR(400MHz,DMSO-d6):δ＝3.40-3.45(d,12H,-P-O-CH3),3.34-3.38(d,2H,-CH-),1.46-1.52(m,2H,-CH-C 2H-CH-).
Preparation example 7
A phosphorus-containing flame retardant with hydroxyl groups has the following structure:
the preparation method comprises the following steps:
adding 2mol of dimethyl phosphite, 1mol of o-phthalaldehyde and 20mL of ethanol into a three-neck flask with a magnetic stirring thermometer, stirring, controlling the temperature to be below 5 ℃ in an ice-water bath, dropwise adding 2mol of triethylamine, gradually heating to reflux, continuously reacting for 1h, and carrying out reduced pressure distillation to obtain the reactive flame retardant with the structure.
1H NMR(400MHz,DMSO-d6):δ＝7.10-7.14(s,4H,ph-H),4.58-4.62(s,2H,-CH-P),3.40-3.45(d,12H,-P-O-CH3).
Preparation example 8
A phosphorus-containing flame retardant with hydroxyl groups has the following structure:
the preparation method comprises the following steps:
adding 1mol of dimethyl phosphite, 1mol of p-hydroxyphenylacetaldehyde and 20mL of ethanol into a three-neck flask with a magnetic stirring thermometer, stirring, controlling the temperature to be below 5 ℃ in an ice-water bath, dropwise adding 2mol of triethylamine, gradually heating to reflux, continuously reacting for 1h, and carrying out reduced pressure distillation to obtain the reactive flame retardant with the structure.
1H NMR(CDCl3400MHz, TMS): δ ═ 9.21-9.45(s, H, -OH),7.01-7.03(d,2H, H with the phenyl ring near-CH-), 6.65-6.68(d,2H, H with the phenyl ring near the hydroxyl group), 4.52-4.55(s,1H, -CH-),3.44-3.48(d,6H, -P-O-CH-), and3).
the phosphorus-containing flame retardant with hydroxyl prepared by the invention is applied to the preparation of polyurethane resin:
examples 1 to 8
A polyurethane particle is prepared by the following steps:
40 parts by weight of phosphorus-containing flame retardant, 100 parts by weight of isophorone diisocyanate, 55 parts by weight of hydroxyl-terminated polytetrahydrofuran having a molecular weight of 2000, 5 parts by weight of ethylene glycol and 1 part by weight of catalyst were mixed and extruded by a twin-screw extruder to obtain polyurethane particles.
Wherein the phosphorus-containing flame retardant is provided in preparation examples 1-8.
Comparative example 1
The phosphorus-containing flame retardant was replaced with a hydroxyl-terminated polytetrahydrofuran having a molecular weight of 2000.
Comparative examples 2 to 3
On the basis of comparative example 1, triphenyl phosphate, which is a flame retardant, was added in an amount of 40 parts by weight (comparative example 2) and 75 parts by weight (comparative example 3).
Performance testing
The polyurethane particles provided in examples 1 to 8 and comparative examples 1 to 3 were subjected to a performance test as follows:
(1) combustibility: testing according to UL-94 vertical burning test standard;
(2) tensile strength and elongation: the method is carried out according to the regulation of GB/T528-2009, the test speed (500 +/-50) mm/min and the thickness of a sample are 10 mm;
(3) flame retardant stability: the polyurethane composition was soaked in water for 1 hour and dried to measure its flammability again.
The results of the tests on the examples and comparative examples are shown in Table 1:
TABLE 1
Sample (I)
Combustibility
Tensile strength/MPa
Elongation at break/%
Combustibility after immersion in water
Example 1
V-0
40.5
210
V-0
Example 2
V-0
39.8
215
V-0
Example 3
V-0
37.8
224
V-0
Example 4
V-0
37.5
229
V-0
Example 5
V-0
42.5
198
V-0
Example 6
V-0
41.6
205
V-0
Example 7
V-0
54.2
175
V-0
Example 8
V-0
55.9
174
V-0
Comparative example 1
V-2
32.1
264
V-2
Comparative example 2
V-1
35.7
174
V-2
Comparative example 3
V-0
36.4
124
V-1
As can be seen from the examples and performance tests, the reactive flame retardant with hydroxyl groups provided by the invention can participate in the preparation process of polyurethane resin, and has stability; meanwhile, the flame retardant property of the material can reach V-0 level, and the phosphorus-containing flame retardant provided by the invention has good flame retardant stability, and the flame retardant property can not be reduced because the flame retardant is dissolved in water in operations such as washing and the like. As is clear from the comparison of examples 1 to 8, the tensile strength of the finally obtained polyurethane resin was high and was 54.2MPa or more when the phosphorus-containing flame retardants provided in preparation examples 7 to 8 were selected, and the elongation at break was good and was 210% or more when the phosphorus-containing flame retardants provided in preparation examples 1 to 4 were selected.
The phosphorus-containing flame retardant with hydroxyl prepared by the invention is applied to the preparation of silicon rubber:
examples 9 to 16
A silicone rubber composition is prepared by the following steps:
60 parts by weight of phenyltrimethoxysilane, 60 parts by weight of vinyltrimethoxysilane, 80 parts by weight of a reactive flame retardant with hydroxyl and 10 parts by weight of benzenesulfonic acid are mixed at 60 ℃ for 8 hours, and then 10 parts by weight of a catalyst is added to be mixed to obtain the silicone rubber.
The phosphorus-containing flame retardants were the phosphorus-containing flame retardants provided in preparation examples 1-8, respectively.
Comparative example 4
The only difference from example 9 was that the reactive flame retardant having hydroxyl groups was replaced with 100 parts by weight of polyphosphate.
And (3) performance testing:
the samples provided in examples 9-16 and comparative example 4 were tested for performance by the following method:
(1) combustibility: testing according to UL-94 vertical burning test standard;
(2) tensile strength and elongation: according to the regulation of GB/T528-2009;
(3) flame retardant stability: after soaking the silicone rubber composition in water for 1h, it was dried and its flammability was measured again.
Test results for examples and comparative examples table 2:
TABLE 2
The embodiment and the performance test show that the phosphorus-containing flame retardant with hydroxyl can participate in the preparation of the silicon rubber, and simultaneously, the phosphorus-containing flame retardant with hydroxyl exists as a molecular chain segment, so that the mechanical property of the silicon rubber can be enhanced, wherein the tensile strength is more than 1.5MPa and can reach more than 1.8 MPa; the flame retardant property of the material can reach V-0 level; the phosphorus-containing flame retardant provided by the invention has good flame retardant stability, and the flame retardant performance can not be reduced because the flame retardant is dissolved in water in operations such as water washing and the like.
The phosphorus-containing flame retardant with hydroxyl prepared by the invention is applied to the preparation of polyester resin:
examples 17 to 24
A polyester composition is prepared by the following steps:
a polyester composition was prepared by mixing 50 parts by weight of maleic anhydride, 10 parts by weight of ethylene glycol, 40 parts by weight of a phosphorus-containing flame retardant having hydroxyl groups, 50 parts by weight of poly (1, 4-cyclohexylenedimethylene) terephthalate, and 10 parts by weight of polyethylene terephthalate.
The phosphorus-containing flame retardants were the phosphorus-containing flame retardants provided in preparation examples 1-8, respectively.
Comparative example 5
The only difference from example 17 was that the reactive flame retardant having a hydroxyl group was replaced with 40 parts by weight of ethylene glycol.
Comparative example 6
The difference from comparative example 5 is that 30 parts by weight of aluminum tris (diethylphosphinate) were added on the basis of comparative example 5.
And (3) performance testing:
the samples provided in examples 17-24 and comparative examples 5-6 were tested for performance by the following method:
(1) combustibility: testing according to UL-94 vertical burning test standard;
(2) tensile strength and elongation: according to the GB/T1040-2006;
(3) flame retardant stability: after soaking the polyester composition in water for 1h, it was dried and its flammability was measured again.
Test results for examples and comparative examples table 3:
TABLE 3
As can be seen from the examples and performance tests, the phosphorus-containing flame retardant with hydroxyl can participate in the preparation of polyester, and simultaneously, the phosphorus-containing flame retardant with hydroxyl exists as a molecular chain segment, so that the mechanical property of the polyester composition can be enhanced, wherein the tensile strength is more than 36.4MPa and can reach more than 37.9 MPa; the flame retardant property of the material can reach V-0 level; the phosphorus-containing flame retardant provided by the invention has good flame retardant stability, and the flame retardant performance can not be reduced because the flame retardant is dissolved in water in operations such as water washing and the like.
The applicant states that the present invention is illustrated by the above examples of the phosphorus-containing flame retardant with hydroxyl groups of the present invention and the preparation method and application thereof, but the present invention is not limited to the above detailed methods, i.e. it does not mean that the present invention must be implemented by relying on the above detailed methods. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
- 上一篇：一种医用注射器针头装配设备
- 下一篇：一种高分子涤纶抗静电剂的制备方法