阅读说明：本技术 阻燃聚合物材料及其合成方法和阻燃铝塑膜 (Flame-retardant polymer material, synthesis method thereof and flame-retardant aluminum-plastic film ) 是由 李义涛 王芳 张魁 杨华军 杨刚 程宗盛 张凌飞 于 2019-08-23 设计创作，主要内容包括：本发明提供了一种阻燃聚合物材料,阻燃聚合物材料包含式(1)或式(2)所示结构单元,<Image he="281" wi="700" file="DDA0002177110820000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image><Image he="292" wi="700" file="DDA0002177110820000012.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>本发明的聚合物材料包括了式(1)或式(2)结构单元,该结构单元形成磷氮协同阻燃体系,使得该阻燃聚合材料的阻燃性能良好和稳定,将该阻燃聚合物材料运用到电池铝塑膜中,能够提供铝塑膜良好和稳定的阻燃性能,使电池能够在一定外界压力和过压充电情况下保持阻燃性能。(The invention provides a flame-retardant polymer material, which comprises a structural unit shown as a formula (1) or a formula (2), the polymer material comprises a structural unit of a formula (1) or a formula (2), and a phosphorus-nitrogen synergistic flame-retardant system is formed by the structural unit, so that the flame-retardant performance of the flame-retardant polymer material is good and stable, and the flame-retardant polymer material is applied to a battery aluminum-plastic film, so that the good and stable flame-retardant performance of the aluminum-plastic film can be provided, and the battery can keep the flame-retardant performance under certain external pressure and overvoltage charging conditions.)

1. A flame retardant polymer material, characterized in that the flame retardant polymer material comprises a structural unit represented by formula (1) or formula (2),

wherein R1 is CnH2n +1, n is a natural number; r2 is CmH2m +1, m is a natural number; r4 is CxH2x +1, x is a natural number; r5 is CyH2y +1, y is a natural number; n1 represents the degree of polymerization of the structural unit represented by the formula (1); n3 the degree of polymerization of the structural unit represented by the formula (2).

2. Flame retardant polymer material according to claim 1, wherein n and m are in the range of 1-8 and x and y are in the range of 1-6.

3. A method for synthesizing a flame-retardant polymer material is characterized by comprising the following steps of:

preparing a compound A, wherein the compound A comprises a structural unit shown as a formula (3),

wherein n2 represents the degree of polymerization of the structural unit represented by formula (3);

preparing a compound B, wherein the compound B comprises a structural unit shown as a formula (4),

wherein R3 is halogen;

and reacting the compound A and the compound B in an organic solvent under the action of a catalyst to generate the flame-retardant polymer material.

4. The method of synthesizing a flame retardant polymeric material of claim 3 wherein said preparing compound A comprises:

adding the nylon film into anhydrous tetrahydrofuran under the protection of nitrogen;

adding 2-6mmol of borane-tetrahydrofuran complex into anhydrous tetrahydrofuran at the temperature of 0-5 ℃, and reacting for 0.5-1.5h at constant temperature;

keeping the temperature for 8-12h at 45-55 ℃.

5. The method of claim 4, wherein the nylon has a number average molecular weight of 19000 and a degree of polymerization of 168.

6. The method for synthesizing flame retardant polymer material according to claim 3, wherein R3 is chlorine, and the preparing compound B comprises:

dissolving neopentyl glycol or a derivative thereof by using dichloromethane to obtain a first solution;

dropwise adding phosphorus oxychloride into the first solution within 1-3h, then heating to 45-55 ℃, and reacting for 4-8 h;

wherein the molar ratio of the neopentyl glycol or the derivative thereof to the phosphorus oxychloride is 1: 1.

7. The method for synthesizing flame-retardant polymer material according to any one of claims 3 to 6, wherein the reaction of the compound A and the compound B in the organic solvent under the action of the catalyst to form the flame-retardant polymer material comprises:

dissolving the compound B and the triethylamine with acetonitrile to form a second solution;

adding the compound A into acetonitrile, dropwise adding the second solution at the temperature of 45-55 ℃ within 1-3h, and then reacting at the temperature of 55-65 ℃ for more than 12 h.

8. The flame-retardant aluminum-plastic film is characterized by comprising a substrate layer, a first bonding layer, an aluminum foil core layer, a second bonding layer and a sealing layer which are sequentially arranged,

the substrate layer comprises a film made of the flame retardant polymer material of any one of claims 1-2; the first bonding layer is a polyurethane adhesive or an epoxy resin adhesive; the aluminum foil core layer is subjected to passivation treatment, wherein the passivation treatment is chromate treatment, zirconium-titanium salt treatment or rare earth oxide treatment; the second bonding layer is a polyolefin adhesive, a polyurethane adhesive or an epoxy resin adhesive; the sealing layer is a thermoplastic resin layer.

9. The flame retardant aluminum plastic film of claim 8, wherein the first bonding layer is a polyurethane adhesive; and/or, the passivation treatment is a chromate treatment; and/or the second bonding layer is a polyolefin adhesive; and/or the sealing layer is CPP.

10. The flame-retardant aluminum-plastic film according to claim 8 or 9, wherein the thickness of the base material layer is 10 to 50 μm; the thickness of the first bonding layer is 2-6 mu m; the thickness of the aluminum foil core layer is 20-60 mu m; the thickness of the second bonding layer is 2-8 mu m; the thickness of the sealing layer is 20-80 mu m.

Technical Field

The invention relates to the field of flame-retardant materials, in particular to a flame-retardant polymer material, a synthetic method thereof and a flame-retardant aluminum-plastic film.

Background

In recent years, the demand of lithium ion batteries on power automobiles is increased in a blowout manner, and higher requirements are put on the safety of the lithium ion batteries. However, safety accidents such as battery combustion and explosion frequently occur due to instability and improper use method of the lithium ion battery, poor battery safety such as thinning and high energy density.

At present, as a packaging film or a packaging shell for protecting the outermost layer of the lithium ion battery, aluminum plastic film packaging (soft package battery) is a commonly used battery packaging type except an aluminum shell and a steel shell, and the soft package battery has the characteristics of light weight, large capacity, small internal resistance and flexible design. The existing aluminum-plastic film package has no flame retardant effect, and the burning of one battery easily causes the burning of other batteries or substances, thereby increasing the insecurity of the battery pack. Therefore, the flame retardant property of the aluminum plastic film is improved by adding a flame retardant externally. For example, patent No. CN 108155307a mentions embedding flame retardant microcapsules in an aluminum plastic film to improve flame retardancy. Patent No. CN 206460979U mentions that diethyl aluminum phosphinate flame retardant is added to a nylon material layer to improve the flame retardant property of an aluminum-plastic film. Although the flame retardant added externally can provide flame retardant performance, the usage amount is large, the compatibility with the material is poor, and the migration is easy, so that the flame retardant function of the battery is gradually lost in the use process, and the flame retardant effect is not durable.

In view of the above, the present invention provides a flame retardant polymer material, a method for synthesizing the same, and a flame retardant aluminum plastic film.

Disclosure of Invention

The present invention aims to overcome the above-mentioned defects of the prior art and provide a flame-retardant polymer material, a synthetic method thereof and a flame-retardant aluminum-plastic film.

The object of the invention can be achieved by the following technical measures:

the invention provides a flame-retardant polymer material, which comprises a structural unit shown as a formula (1) or a formula (2),

wherein R1 is CnH2n +1, n is a natural number; r2 is CmH2m +1, m is a natural number; r4 is CxH2x +1, x is a natural number; r5 is CyH2y +1, y is a natural number; n1 represents the degree of polymerization of the structural unit represented by the formula (1); n3 the degree of polymerization of the structural unit represented by the formula (2).

Further, n and m are in the range of 1 to 8, and x and y are in the range of 1 to 6.

The invention also provides a synthesis method of the flame-retardant polymer material, which comprises the following steps:

preparing a compound A, wherein the compound A comprises a structural unit shown as a formula (3),

wherein n2 represents the degree of polymerization of the structural unit represented by formula (3);

preparing a compound B, wherein the compound B comprises a structural unit shown as a formula (4),

wherein R3 is halogen;

and reacting the compound A and the compound B in an organic solvent under the action of a catalyst to generate the flame-retardant polymer material.

Further, the preparation of compound a comprises:

adding the nylon film into anhydrous tetrahydrofuran under the protection of nitrogen;

adding 2-6mmol of borane-tetrahydrofuran complex into anhydrous tetrahydrofuran at the temperature of 0-5 ℃, and reacting for 0.5-1.5h at constant temperature;

keeping the temperature for 8-12h at 45-55 ℃.

Further, the number average molecular weight (Mn) of the nylon was 19000, and the polymerization degree of the nylon was 168.

Further, R3 is chloro, and the preparing compound B comprises:

dissolving neopentyl glycol or a derivative thereof by using dichloromethane to obtain a first solution;

dropwise adding phosphorus oxychloride into the first solution within 1-3h, then heating to 45-55 ℃, and reacting for 4-8 h;

wherein the molar ratio of the neopentyl glycol or the derivative thereof to the phosphorus oxychloride is 1: 1.

Further, the compound a and the compound B react in an organic solvent under the action of a catalyst to form a flame-retardant polymer material, which comprises:

dissolving the compound B and the triethylamine with acetonitrile to form a second solution;

adding the compound A into acetonitrile, dropwise adding the second solution at the temperature of 45-55 ℃ within 1-3h, and then reacting at the temperature of 55-65 ℃ for more than 12 h.

The invention also provides a flame-retardant aluminum-plastic film, which comprises a substrate layer, a first bonding layer, an aluminum foil core layer, a second bonding layer and a sealing layer which are arranged in sequence,

the substrate layer comprises a film made of the flame-retardant polymer material; the first bonding layer is a polyurethane adhesive or an epoxy resin adhesive; the aluminum foil core layer is subjected to passivation treatment, wherein the passivation treatment is chromate treatment, zirconium-titanium salt treatment or rare earth oxide treatment; the second bonding layer is a polyolefin adhesive, a polyurethane adhesive or an epoxy resin adhesive; the sealing layer is a thermoplastic resin layer.

Further, the first bonding layer is a polyurethane adhesive; and/or, the passivation treatment is a chromate treatment; and/or the second bonding layer is a polyolefin adhesive; and/or the sealing layer is CPP.

Further, the thickness of the base material layer is 10-50 μm; the thickness of the first bonding layer is 2-6 mu m; the thickness of the aluminum foil core layer is 20-60 mu m; the thickness of the second bonding layer is 2-8 mu m; the thickness of the sealing layer is 20-80 mu m.

The flame-retardant polymer material has the beneficial effects that the polymer material comprises the structural unit shown in the formula (1) or the formula (2), a phosphorus-nitrogen synergistic flame-retardant system is formed by the structural unit, so that the flame-retardant performance of the flame-retardant polymer material is good and stable, and the flame-retardant polymer material is applied to the aluminum plastic film of the battery, so that the good and stable flame-retardant performance of the aluminum plastic film can be provided, and the battery can keep the flame-retardant performance under certain external pressure and over-voltage charging.

Drawings

Fig. 1 is a schematic structural diagram of an aluminum plastic film according to an embodiment of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

In order to make the description of the present disclosure more complete and complete, the following description is given for illustrative purposes with respect to the embodiments and examples of the present invention; it is not intended to be the only form in which the embodiments of the invention may be practiced or utilized. The embodiments are intended to cover the features of the various embodiments as well as the method steps and sequences for constructing and operating the embodiments. However, other embodiments may be utilized to achieve the same or equivalent functions and step sequences.

Preparation of flame-retardant nylon

1. Synthesis of compound a:

adding a nylon film into 25mL of anhydrous tetrahydrofuran, and filling nitrogen for protection, wherein the Mn of the nylon is 19000, and the polymerization degree is 168;

then introducing 2-6mL of borane-tetrahydrofuran complex of 1mol/L by using an injector under the condition that the temperature is 0-5 ℃ (preferably 0 ℃), and reacting for 0.5-1.5h at constant temperature;

then raising the temperature to 45-55 ℃ (preferably 50 ℃), and preserving the temperature for 8-12 h;

and (3) taking out the nylon film, sequentially washing the nylon film with tetrahydrofuran, hydrochloric acid (1mol/L), deionized water, sodium hydroxide (1mol/L), deionized water, tetrahydrofuran, ethanol and n-hexane, and then placing the nylon film in a vacuum drying oven at 50 ℃ for drying for 24 hours to obtain a product A, wherein the product A is the compound A, and the specific chemical reaction is shown in a reaction equation I.

The reaction equation one:

2. synthesis of compound B:

synthesis of Compounds B-I

Adding 3.70g (0.05mol) of anhydrous n-butanol and 2.30g (0.05mol) of anhydrous ethanol into 100mL of dichloromethane, starting magnetic stirring, and heating to 30-40 ℃ to form a first solution;

then slowly dripping 15.30g (0.1mol) of phosphorus oxychloride (the chlorine in the phosphorus oxychloride can also be other halogen) for 1-3h under the protection of nitrogen, and then heating to 45-55 ℃ for reacting for 4-8 h;

after the reaction is finished, removing a dichloromethane solvent through vacuum filtration, washing the obtained white solid for 3 times by using a normal hexane solvent, and then placing the white solid in a blowing oven at the temperature of 80 ℃ to dry the white solid to constant weight to obtain a product B-I, wherein the product B-I is a compound B-I, and the specific chemical reaction is shown in a reaction equation II.

The reaction equation two:

synthesis of Compounds B-II

Adding 10.42g (0.1mol) of neopentyl glycol subjected to vacuum overnight treatment into 100mL of dichloromethane, stirring and dissolving, starting magnetic stirring, and heating to 30-40 ℃ to form a first solution;

then slowly dripping 15.30g (0.1mol) of phosphorus oxychloride (the chlorine in the phosphorus oxychloride can also be other halogen) for 1-3h under the protection of nitrogen, and then heating to 45-55 ℃ for reacting for 4-8 h;

after the reaction is finished, removing the dichloromethane solvent through vacuum filtration, washing the obtained white solid for 3 times by using the n-hexane solvent, and then placing the white solid in a blowing oven at the temperature of 80 ℃ to dry the white solid to constant weight to obtain a product B-II, wherein the product B-II is a compound B-II, and the specific chemical reaction is shown in a reaction equation III.

The reaction equation three:

3. synthesis of compound C:

dissolving the product B (B-I, B-II) and an acid-binding agent triethylamine in 10mL of acetonitrile to form a second solution;

adding the product A into 50mL of acetonitrile solution, and finishing dropwise adding (preferably dropwise adding for 2h) the second solution within 1-3h at the temperature of 45-55 ℃ (preferably 50 ℃);

then raising the temperature to 55-65 ℃ (preferably 60 ℃), and keeping the temperature for reaction for more than 12h (preferably 12 h);

and after the reaction is finished, taking out the film, sequentially washing the film by using ethanol, acetone, n-hexane and deionized water, and then placing the film in a vacuum drying oven at 50 ℃ for drying for 24 hours to obtain a product C, wherein the product C is the modified nylon material compound C, and the specific chemical reaction is shown in reaction equations four and five.

The reaction equation four:

the reaction equation five:

the invention provides a flame-retardant polymer material through the preparation process, which comprises a structural unit shown as a formula (1) or a formula (2),

r1 is CnH2n +1, n is a natural number; r2 is CmH2m +1, m is a natural number; r4 is CxH2x +1, x is a natural number; r5 is CyH2y +1, and y is a natural number. Wherein, R1, R2, R4 and R5 may be the same or different, and may have a straight chain structure or a branched structure.

n1 represents the degree of polymerization of the structural unit represented by the formula (1); a degree of polymerization of a structural unit represented by formula (2) n 3; n and m are in the range of 1-8, and x and y are in the range of 1-6. If the alkyl chain is too long, the steric hindrance of the reaction is large and it is difficult to graft the polymer chain as a branch.

In some embodiments, n and m are in the range of 1 to 6; in some embodiments, n and m are in the range of 1 to 4, which may list: methyl, ethyl, n-propyl, isopropyl, n-butyl.

In some embodiments, x and y are in the range of 1 to 4, which may list: methyl, ethyl, n-propyl, isopropyl, n-butyl. The flame-retardant polymer of formula (1) can also be reduced to a compound A with a secondary amine bond by reacting a nylon material with a borane-tetrahydrofuran complex, a compound B is formed by reacting an alcohol char-forming agent with phosphorus oxychloride, and the compound A and the compound B react under the action of a catalyst to form a compound C containing formula (1).

The flame-retardant polymer of formula (2) is prepared by the preparation process, and the chemical formula of the compound B isAnd when x is 1 and y is 1, the compound B isThe compound C is

Secondly, preparing the aluminum plastic film:

the structure of the flame-retardant aluminum-plastic film is shown in fig. 1, and the flame-retardant aluminum-plastic film sequentially comprises a substrate layer 1, a bonding resin layer 2, an aluminum foil core layer 3, a bonding resin layer 4 and a sealing layer 5.

The substrate layer 1 is a thin film layer made of a compound C, and the thickness of the thin film layer is 10-50 micrometers, preferably 25 micrometers; the bonding resin layer 2 is made of one of polyurethane adhesive and epoxy resin adhesive, the polyurethane adhesive is preferred, and the thickness of the bonding layer is 2-6 microns, preferably 4 microns; the aluminum foil core layer 3 is subjected to passivation treatment, wherein the passivation treatment is one of chromate treatment, zirconium titanium salt treatment and rare earth oxide treatment, preferably chromate treatment, and the thickness of the aluminum foil is 20-60 mu m, preferably 40 mu m; the adhesive resin layer 4 is one of polyolefin adhesive, polyurethane adhesive and epoxy resin adhesive, preferably polyolefin adhesive, and the thickness of the adhesive layer is 2-8 μm, preferably 4 μm; the sealing layer 5 is a thermoplastic resin layer, preferably CPP, and the thickness of the sealing layer is 20-80 μm, preferably 40 μm.

The principle of the reaction is that an amido bond on nylon is chemically reduced by a borane-tetrahydrofuran complex to obtain a secondary amine group with high reaction activity, then a phosphorus-containing reaction intermediate of 2-chloro-2-oxo-5, 5-dimethyl-1, 3, 2-dioxaphosphorinane is synthesized, finally the phosphorus-containing reaction intermediate reacts with the secondary amine group, a phosphorus-containing flame retardant group is introduced onto a nylon molecule to form a phosphorus-nitrogen synergistic flame retardant system, and a nylon material with a flame retardant function is prepared, so that the flame retardant performance of the aluminum plastic film is improved. The modified nylon material prepared by the invention has good and stable flame retardant property, thereby providing good and stable flame retardant property for the aluminum plastic film, and being capable of keeping the flame retardant property under certain external pressure and overvoltage charging condition.

Based on the above preparations, several specific examples are described below, by adjusting the synthesis conditions during the synthesis of compound A and compound B (using optimum conditions with optimum conditions), compound A (A1, A2, A3 and A4) and compound B (B-II1, B-II2, B-II3 and B-I1) were obtained in different purities. The obtained compounds A (A1, A2, A3 and A4) and B (B-II1, B-II2, B-II3 and B-I1) react to synthesize compounds C (C1, C2, C3 and C4) with different grafting ratios, and the flame retardant properties of the obtained compounds C (C1, C2, C3 and C4) are respectively tested. The final aluminum-plastic film packaged battery is tested for flame retardant performance by preparing aluminum-plastic films from different compound C (C1, C2, C3 and C4) materials.