CN112210322B

CN112210322B - Composition for bonding glass and laminated glass containing same

Info

Publication number: CN112210322B
Application number: CN201910632011.4A
Authority: CN
Inventors: 杨建春; 杨冬梅; 宴成强; 汪帆
Original assignee: Beijing Nuowei New Material Technology Co ltd
Current assignee: Beijing Nuowei New Material Technology Co ltd
Priority date: 2019-07-12
Filing date: 2019-07-12
Publication date: 2021-09-28
Anticipated expiration: 2039-07-12
Also published as: WO2021008254A1; CN112210322A

Abstract

The invention discloses a glass bonding composition and a laminated glass containing the same. The composition comprises a polyhydroxy polymer and a filler, wherein the polyhydroxy polymer is 50-99.99 parts by weight, and the filler is 0.01-50 parts by weight; the polyhydroxy polymer contains at least ortho-dihydroxy. The bonding composition has strong bonding force with glass, and the laminated glass prepared by using the material as an intermediate adhesive layer has good light transmission, good impact resistance and strong moisture resistance.

Description

Composition for bonding glass and laminated glass containing same

Technical Field

The invention belongs to the technical field of glass bonding materials, and relates to a glass bonding composition and laminated glass containing the same.

Background

In order to achieve the purposes of safety, heat preservation, noise control, ultraviolet isolation and the like, the laminated glass is more and more widely applied to industries such as buildings, automobiles and the like. The laminated glass is a composite glass product which is formed by two or more pieces of glass, wherein one or more layers of organic polymer intermediate films are sandwiched between the two or more pieces of glass, and the glass and the intermediate films are permanently bonded into a whole after special high-temperature prepressing (or vacuumizing) and high-temperature high-pressure processing.

Commonly used interlayer films for laminated glass include: polyvinyl butyral (PVB), an ionic interlayer (SGP) mainly composed of an ethylene-methacrylate copolymer, an ethylene-vinyl acetate copolymer (EVA), Polyurethane (PU), and the like.

PVB has good safety, sound insulation, transparency and ultraviolet resistance, but PVB has poor water resistance and is easy to be stripped and fall off when being in a humid environment for a long time. EVA has good water resistance, but has weak ultraviolet resistance, and is easy to yellow and black after being exposed to the sun for a long time, so that the EVA is mainly used for indoor partition. SGP is a high-performance sandwich material developed by DuPont, and has better mechanical properties, stability and moisture resistance than PVB. Although the production process of SGP is close to that of PVB, the terminal price is high, so that the SGP is not widely applied in China.

Plasticized PVB films have a high surface tack and can have a separation problem when wound after film formation. In addition, the production of plasticized polyvinyl butyral films requires special equipment, which, due to the sensitivity to moisture, must generally be operated under controlled atmospheric conditions during the preparation, storage and ready incorporation into laminated safety glass. All of this adds to the cost of making laminated glass from PVB film.

Disclosure of Invention

The application provides a glass bonding composition containing polyhydroxy polymer, a preparation method thereof and laminated glass containing the composition. The polyhydroxy polymer has strong adhesion to glass, and the laminated glass prepared by using the polymer as an intermediate adhesive layer has good light transmission, good impact resistance and strong moisture resistance.

The purpose of the invention is realized by the following technical scheme:

the first aspect of the invention provides a glass bonding composition, which comprises 50-99.99 parts of polyhydroxy polymer and 0.01-50 parts of filler by weight;

the polyhydroxy polymer at least contains ortho-dihydroxy, and comprises a structural unit shown in a formula (I) and optionally structural units shown in a formula (II), a formula (III) and a formula (IV):

in the formula (I), R₁、R₂、R₃、R₄、R₅And R₆Same or different, independently from each other selected from H, C_1-8Alkyl, unsubstituted or optionally substituted by one, two or more R_aSubstituted C_6-20An aryl group; each R_aIdentical or different, independently of one another, from C_1-12An alkyl group;

a. b, c, d, e and f are each independently an integer of 0 or more, and a and e are not 0 at the same time;

in the formula (II), R₁₉Selected from H, cyano, C_1-8Alkyl, unsubstituted or optionally substituted by one, two or more R_aSubstituted of the following groups: c_3-10Cycloalkyl radical, C_6-20An aryl group; each R_aIdentical or different, independently of one another, from C_1-12An alkyl group;

g is an integer of 1 or more;

in the formula (III), R₁₃、R₁₆、R₁₇And R₁₈Same or different, independently from each other selected from H, C_1-8Alkyl, unsubstituted or optionally substituted by one, two or more R_aSubstituted C_6-20An aryl group; each R_aIdentical or different, independently of one another, from C_1-12An alkyl group;

h. i, j, k are independently integers of 0 or more; n' is an integer of 1 or more;

in the formula (IV), R₇、R₈、R₉、R₁₀、R₁₁And R₁₂Same or different, independently from each other selected from H, C_1-8Alkyl, unsubstituted or optionally substituted by one, two or more R_aSubstituted C_6-20An aryl group; each R_aIdentical or different, independently of one another, from C_1-12An alkyl group;

a ', b', c ', d', e 'and f' are independent integers not less than 0 and not simultaneously 0.

The polymer may be a homopolymer, a random copolymer, or a block copolymer.

Wherein R is₁、R₂、R₃、R₄、R₅And R₆Same or different, independently from each other selected from H, C_1-4Alkyl, unsubstituted or optionally substituted by one, two or more R_aSubstituted C_6-10An aryl group; r_aThe definition of (A) is as above.

Wherein R is₁、R₂、R₃、R₄、R₅And R₆Identical or different, independently of one another, from the group consisting of H, methyl, phenyl, tolyl. Preferably, R₁、R₂、R₃、R₄、R₅And R₆Identical or different, independently of one another, from H, methyl. Also preferably, R₁、R₂、R₃、R₄、R₅And R₆And the same, is selected from H.

Wherein R is₁₉Selected from H, cyano, C_1-4Alkyl, unsubstituted or optionally substituted by one, two or more R_aSubstituted C_6-10An aryl group; r_aThe definition of (A) is as above. For example, R₁₉Selected from phenyl, tolyl, cyano.

Wherein R is₇、R₈、R₉、R₁₀、R₁₁And R₁₂Same or different, independently from each other selected from H, C_1-4Alkyl, unsubstituted or optionally substituted by one, two or more R_aSubstituted C_6-10An aryl group; r_aThe definition of (A) is as above. For example, R₇、R₈、R₉、R₁₀、R₁₁And R₁₂Identical or different, independently of one another, from the group consisting of H, methyl, phenyl, tolyl. Preferably, R₇、R₈、R₉、R₁₀、R₁₁And R₁₂Identical or different, independently of one another, from H, methyl. Also preferably, R₇、R₈、R₉、R₁₀、R₁₁And R₁₂And the same, is selected from H.

Wherein R is₁₃、R₁₆、R₁₇And R₁₈Same or different, independently from each other selected from H, C_1-4Alkyl, unsubstituted or optionally substituted by one, two or more R_aSubstituted C_6-10An aryl group; r_aThe definition of (A) is as above. For example, R₁₃、R₁₆、R₁₇And R₁₈Identical or different, independently of one another, from the group consisting of H, methyl, phenyl, tolyl. Preferably, R₁₃、R₁₆、R₁₇And R₁₈Identical or different, independently of one another, from H, methyl. Also preferably, R₁₃、R₁₆、R₁₇And R₁₈And the same, is selected from H.

Wherein a is an integer between 0 and 20000, such as a is 1, 50, 500, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 12000, 15000, 18000 or 20000, such as a is an integer between 1 and 7000; preferably, a is an integer between 50 and 3000.

Wherein b is an integer between 0 and 2000 (e.g., 1, 5, 50, 100, 500, 1000, 1500, or 2000), c is an integer between 0 and 2000 (e.g., 1, 5, 50, 100, 500, 1000, 1500, or 2000), d is an integer between 0 and 2000 (e.g., 1, 5, 50, 100, 500, 1000, 1500, or 2000), e is an integer between 0 and 20000 (e.g., 1, 50, 500, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 12000, 15000, 18000, or 20000), and f is an integer between 0 and 2000 (e.g., 1, 5, 50, 100, 500, 1000, 1500, or 2000).

Wherein g is an integer between 1 and 10000 (e.g., 1, 50, 500, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, or 10000).

Wherein a 'is an integer between 0 and 20000 (e.g. 1, 50, 500, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 12000, 15000, 18000 or 20000), b' is an integer between 0 and 2000 (e.g. 1, 5, 50, 100, 500, 1000, 1500 or 2000), c 'is an integer between 0 and 2000 (e.g. 1, 5, 50, 100, 500, 1000, 1500 or 2000), d' is an integer between 0 and 2000 (e.g. 1, 5, 50, 100, 500, 1000, 1500 or 2000), e 'is an integer between 0 and 10000 (e.g. 1, 50, 500, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000 or 10000), f' is an integer between 0 and 2000 (e.g. 1, 5, 50, 100, 500, 1000, 1500 or 2000). Preferably, a 'and e' are not both 0 at the same time.

Wherein h is an integer between 0 and 2000 (e.g., 1, 5, 50, 100, 500, 1000, 1500, or 2000), i is an integer between 0 and 2000 (e.g., 1, 5, 50, 100, 500, 1000, 1500, or 2000), j is an integer between 0 and 2000 (e.g., 1, 5, 50, 100, 500, 1000, 1500, or 2000), and k is an integer between 0 and 2000 (e.g., 1, 5, 50, 100, 500, 1000, 1500, or 2000).

Wherein n' is an integer between 1 and 10 (e.g., 1,2, 3, 4, 5, 6, 7, 8, 9, or 10). Preferably, n' is 1 or 2.

According to the invention, the polyhydroxylated polymer is 50 to 99.99 parts, preferably 55 to 95 parts, still preferably 60 to 90 parts, more preferably 65 to 85 parts, by weight; illustratively, the polyol polymer is 70 parts, 75 parts, 80 parts.

According to the invention, the filler is present in an amount of 0.01 to 50 parts, preferably 5 to 45 parts, still preferably 10 to 40 parts, more preferably 15 to 35 parts, by weight; illustratively, the filler is 0.1 parts, 0.5 parts, 2 parts, 5 parts, 5.5 parts, 20 parts, 25 parts, 30 parts.

According to the present invention, the filler is selected from at least one of a plasticizer, an antioxidant, an ultraviolet absorber, a dispersant, a pigment, silica, and the like. Wherein the plasticizer may be selected from at least one of triethylene glycol diisocaprylate, dipentaerythritol ester, ethylene glycol ester and triethylene glycol di (2-ethylbutyrate), for example, triethylene glycol diisocaprylate, dipentaerythritol ester or ethylene glycol ester; the antioxidant can be selected from Pasteur antioxidant 1010 and/or Pasteur antioxidant 168; the ultraviolet resistant absorbent can be at least one selected from UV-326, UV-P and T-P, for example, UV-326, UV-P or T-P can be selected; the dispersant can be selected from polymer dispersant GR-5100H; the organic pigment can be phthalocyanine blue, phthalocyanine green, pink, carbon black or permanent yellow; the silica may be selected from fumed silica, preferably having a particle size of 7-40 nm. Preferably, the filler comprises 0-50 parts of plasticizer, 0-2 parts of antioxidant, 0-2 parts of anti-ultraviolet absorbent, 0-8 parts of dispersant, 0-10 parts of pigment and 0-10 parts of silicon dioxide by weight.

Illustratively, the polymer may have any one of the structures shown by the following formulas (1) and (2):

a, d, g have the value ranges as described above.

According to an embodiment of the present invention, the composition comprises a polymer represented by formula (1) and/or formula (2), and a filler; the polymer accounts for 50 to 99.99 parts by weight, and the filler accounts for 0.01 to 50 parts by weight; the filler is selected from antioxidants and/or plasticizers.

According to the invention, the molar content of ortho-dihydroxy polymer structural units in the polyhydroxyl polymer is from 20 to 100%, for example from 23 to 98%, from 25 to 80%, and may be, for example, from 24.7%, 30.6%, 45%, 62%, 98%.

According to the invention, the number average molecular weight of the polyhydroxyl polymer is from 1 to 22 ten thousand, preferably from 2 to 20 ten thousand, for example from 5 to 20 ten thousand, for example from 6 to 20 ten thousand, illustratively the number average molecular weight is from 13.3 to 14.6 ten thousand.

In a second aspect of the invention, there is provided a glass bonding material comprising the above composition.

According to the present invention, the form of the glass bonding material is not limited, and may be, for example, a film, a bead, or the like.

A third aspect of the present invention provides a method for producing the above-described glass bonding material, comprising the steps of:

and dissolving the polyhydroxy polymer in an organic solvent, adding a filler, and drying to obtain the glass bonding material.

The organic solvent may be at least one of dimethyl sulfoxide, acetic acid, ethanol, etc., and is preferably dimethyl sulfoxide.

Wherein the mass concentration of the mixed solution formed by the polyhydroxy polymer, the organic solvent and the filler is 1-90%, for example, 10-80%, for example, 20-70%, and for example, 30-60%; illustratively, the mass concentration is 50%. Preferably, in the mixed solution, the polyhydroxy polymer and the filler have the meaning and mass ratio as described above.

Wherein the drying temperature may be 50-200 deg.C, such as 75-85 deg.C, and may be 80 deg.C as an example.

According to an exemplary embodiment of the present invention, the method for preparing the glass bonding material may include the steps of:

(1) dissolving the polyhydroxy polymer in dimethyl sulfoxide to prepare a dimethyl sulfoxide solution of the polymer;

(2) adding the filler into the polymer dimethyl sulfoxide solution obtained in the step (1), and uniformly stirring;

(3) putting the uniform mixture obtained in the step (2) into a shallow groove (such as a polyethylene shallow groove), removing a dimethyl sulfoxide solvent, and drying to obtain a membrane layer;

(4) and (4) taking out the film layer obtained in the step (3), and stretching the film layer by using a stretcher to prepare the polymer film.

A fourth aspect of the invention provides the use of a glass bonding material as described above in laminated glass.

A fifth aspect of the present invention provides a laminated glass containing the above-described glass bonding material.

A sixth aspect of the present invention provides a method for producing the laminated glass described above, comprising the steps of: and adding the glass bonding material between two pieces of glass, pressurizing, and pressing at 25-150 ℃ for 5-40 minutes to prepare the laminated glass.

Wherein the pressurization requires a pressure of up to 0.1-15kg pressure, such as 0.8-8kg pressure, illustratively 1kg pressure.

Among them, the temperature is preferably 30 to 145 ℃ such as 135 ℃.

Among them, the pressing time is preferably 5 to 35 minutes, for example, 30 minutes.

Terms and explanations:

the term "C_1-12Alkyl is understood to preferably mean a straight-chain or branched, saturated monovalent hydrocarbon radical having from 1 to 12 carbon atoms, preferably C_1-8An alkyl group. "C_1-8Alkyl "is understood to preferably mean a straight-chain or branched, saturated monovalent hydrocarbon radical having 1,2, 3, 4, 5, 6, 7 or 8 carbon atoms. The alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a 2-methylbutyl group, a 1-ethylpropyl group, a 1, 2-dimethylpropyl group, a neopentyl group, a 1, 1-dimethylpropyl group, a 4-methylpentyl group, a 3-methylpentyl group, a 2-ethylbutyl group, a 1-ethylbutyl group, a 3, 3-dimethylbutyl group, a 2, 2-dimethylbutyl group, a 1, 1-dimethylbutyl group, a 2, 3-dimethylbutyl group, a 1, 3-dimethylbutyl group or a 1, 2-dimethylbutyl group, or the like, or isomers thereof. In particular, the radicals have 1,2, 3, 4, 5 or 6 carbon atoms ("C)_1-6Alkyl groups) such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, more particularly groups having 1,2 or 3 carbon atoms ("C)_1-3Alkyl groups) such as methyl, ethyl, n-propyl or isopropyl.

The term "C_6-20Aryl "is understood to preferably mean a mono-, bi-or tricyclic hydrocarbon ring having a monovalent or partially aromatic character with 6 to 20 carbon atoms, preferably" C_6-14Aryl ". The term "C_6-14Aryl "is to be understood as preferably meaning a mono-, bi-or tricyclic hydrocarbon ring having a monovalent or partially aromatic character with 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms (" C_6-14Aryl group "), in particular a ring having 6 carbon atoms (" C₆Aryl "), such as phenyl; or biphenyl, or is a ring having 9 carbon atoms ("C₉Aryl), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C₁₀Aryl radicals ") For example tetrahydronaphthyl, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms ("C)₁₃Aryl radicals), such as the fluorenyl radical, or a ring having 14 carbon atoms ("C)₁₄Aryl), such as anthracenyl.

The invention has the beneficial effects that:

the invention provides a glass bonding composition containing polyhydroxy polymer and a laminated glass containing the bonding composition. The bonding composition has strong bonding force with glass, and the laminated glass prepared by using the material as an intermediate adhesive layer has good light transmission, good impact resistance and strong moisture resistance.

Drawings

FIG. 1 is a graph comparing the moisture resistance of laminated glass comprising the polymer of preparation example 1 with that of PVB laminated glass.

FIG. 2 is a graph of the water absorption properties of polymer films and PVB films of preparation 1, preparation 2 and preparation 3.

Detailed Description

The composition of the present invention comprises a polymer containing multiple hydroxyl groups, which can be prepared by a process comprising the steps of:

(i) preparing an epoxidized polymer by carrying out an oxidation reaction on a polymer containing a structural unit shown as a formula (V),

in formula (V), x is a + b + c, and y is d + e + f; r₁、R₂、R₃、R₄、R₅、R₆A, b, c, d, e and f are as defined above;

(ii) and hydrolyzing the epoxidized polymer, or hydrolyzing and then carrying out catalytic hydrogenation reaction, or carrying out catalytic hydrogenation reaction and then hydrolyzing, thus obtaining the polymer product.

Wherein, the polymer containing the structural unit shown in the formula (V) can also contain at least one of the structural units shown in the formulas (II), (VI) and (VII):

in the formula (II), R₁₉And g is as defined above;

in the formula (VI), n ═ h + i + j + k, R₁₃、R₁₆、R₁₇、R₁₈H, i, j, k and n' are as defined above;

in formula (VII), x '+ a' + b '+ c', y '+ d' + e '+ f'; r₇、R₈、R₉、R₁₀、R₁₁、R₁₂A ', b', c ', d', e 'and f' are as defined above.

Wherein, in step (i), the polymer containing the structural unit represented by formula (V) may be obtained by polymerizing a conjugated diene monomer, such as 1, 3-butadiene, 1, 3-pentadiene or isoprene.

In step (i), the polymer comprising structural units of formula (V) and at least one structural unit of formula (II) and/or (VI) is prepared by reacting a conjugated diene monomer with at least one R₁₉-CH＝CH₂And/or

The structural monomer is copolymerized, the conjugated diene monomer can be 1, 3-butadiene, 1, 3-pentadiene or isoprene, and R₁₉、R₁₃、R₁₆、R₁₇、R₁₈And n' is as defined above.

In step (i), the polymer comprising structural units of formula (V) and at least one structural unit of formula (VII) is obtained by copolymerization of at least two conjugated diene monomers, such as 1, 3-butadiene, 1, 3-pentadiene or isoprene.

In step (i), the polymer comprising structural units of formula (V), at least one structural unit of formula (VII) and at least one structural unit of formula (II) and/or (VI) is prepared by reacting at least two conjugated diene monomers with at least one R₁₉-CH＝CH₂And/or

Specifically, the preparation method of the polymer containing the structural unit shown in the formula (V) is as follows:

mixing a conjugated diene (such as 1, 3-butadiene, 1, 3-pentadiene or isoprene) with an alkane, an arene or a mixture of the two (such as a toluene-heptane mixture) by a continuous solution polymerization method, adding an initiator (such as nickel naphthenate-BF) at 30-65 deg.C₃-Et₃Al), optionally adding a molecular weight regulator (such as alcohols like octanol) to regulate the molecular weight, and adding a reaction terminator (such as ethanol) to terminate the reaction, thereby preparing the polymer containing the structural unit shown in the formula (V).

Wherein, in step (i), the oxidation reaction includes, but is not limited to, a chlorohydrin process, a peroxide epoxidation process, or an oxygen direct oxidation process. The oxidation reaction is an epoxidation reaction, and the oxidation reaction can be partial epoxidation or full epoxidation.

Illustratively, the peroxide can be selected from one or more of hydrogen peroxide, peroxyformic acid, peroxyacetic acid, peroxybenzoic acid, m-chloroperoxybenzoic acid, tert-butyl hydroperoxide, etc.

Illustratively, the oxidation reaction may be carried out in an organic solvent containing a polymer, or in an emulsion of water/organic solvent, the organic solvent including, but not limited to, aliphatic alkanes, halogenated aliphatic hydrocarbons, aromatic hydrocarbons, cycloalkanes, solvent oils, etc., preferably hexane, cyclohexane, heptane, dichloromethane, benzene, toluene, solvent oils, etc. The temperature of the oxidation reaction is 0-120 ℃, and preferably 20-80 ℃.

Wherein, in the step (ii), the catalytic hydrogenation can open the epoxy ring of the epoxidized polymer by a catalytic hydrogenation method or the like to obtain a polymer containing a hydroxyl group in a C-C chain; the hydrolysis may be carried out by hydrolyzing the epoxidized polymer with a conventional acidic or basic substance to open the epoxy ring to obtain a polymer having a vicinal dihydroxyl group in the C-C chain. The catalytic hydrogenation can be partial catalytic hydrogenation or complete catalytic hydrogenation, and the hydrolysis can be partial hydrolysis or complete hydrolysis. The specific reaction conditions and material ratios of the catalytic hydrogenation and hydrolysis are all conventional in the art, and are not particularly limited as long as the polymer having the structural unit represented by formula (I) of the present application can be prepared.

Illustratively, the acidic substance includes an aqueous hydrogen halide solution, sulfuric acid, nitric acid, or like inorganic acid; organic acids such as alkylsulfonic acids; a solid acid; heteropolyacids and the like.

Illustratively, the alkaline substance includes an aqueous solution of a hydroxide or carbonate of an alkali metal.

Illustratively, the catalytic hydrogenation is carried out under catalysis of raney nickel, triphenylphosphine rhodium chloride or platinum, palladium, and the like.

Illustratively, the catalytic hydrogenation reaction may be carried out in an organic solvent containing a polymer, or in an emulsion of water/organic solvent, wherein the organic solvent includes, but is not limited to, aliphatic alkane, halogenated aliphatic hydrocarbon, cycloalkane, mineral spirit, cyclic ether compound, alcohol, etc., preferably hexane, cyclohexane, tetrahydrofuran, methanol, ethanol, etc. The temperature of the catalytic hydrogenation reaction is 0-120 ℃, and preferably 20-80 ℃.

Illustratively, the hydrolysis reaction may be carried out in an organic solvent containing a polymer, including but not limited to aliphatic alkanes, halogenated aliphatic hydrocarbons, aromatic hydrocarbons, cycloalkanes, mineral spirits, cyclic ether compounds, sulfoxides, sulfones, pyrrolidones, methylpyrrolidones, and the like, preferably tetrahydrofuran, dimethyl sulfoxide, methylpyrrolidones, and the like, and may also be carried out in an emulsion of water/organic solvent. The temperature of the hydrolysis reaction is-20 to 150 ℃, and preferably-10 to 80 ℃.

The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.

The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.

Apparatus and device

Physical structure testing¹HNMR used a JOEL 600 Mm pulse Fourier transform nuclear magnetic resonance spectrometer;

tg value test was determined using TA corporation Q100 differential scanning calorimeter;

the polymer molecular weight was measured by Agilent PL-GPC50 (configured differential refractive index detector and evaporative light scattering detector);

the light transmittance was measured by an ultraviolet-visible spectrophotometer UV3600 (shimadzu corporation, japan).

Preparation example 1

Poly (butadiene): a commercially available polybutadiene block (obtained from Sichuan petrochemical Co., Ltd., structure of formula IV, 1, 4-cis content of about 98%, and 1, 4-trans and 1, 2-structures of about 2%; number average molecular weight)

) And cutting into colloidal particles of about 2 mm.

Epoxidation: in a 250ml three-necked flask equipped with a stirrer and a thermometer, 7g of the above-mentioned polycistronic acid micelle and 100ml of methylene chloride were charged.Dissolving in constant temperature water bath at room temperature, stirring, and introducing nitrogen for several minutes when the solution is completely dissolved into a viscous state. Adding 9.90g of formic acid, and dropwise adding 21.40g of 30% aqueous hydrogen peroxide while stirring; the reaction is continued for about 15hr under heat preservation,¹HNMR(CDCl₃) The peak of the characteristic chemical shift of the 1, 4-cis double bond disappeared (the characteristic chemical shift δ of the epoxy group was 2.98 and the characteristic chemical shift δ of the 1, 4-cis double bond was 5.40). Neutralizing the reaction product with 10% sodium carbonate solution to pH 7, separating water phase, water washing, separating liquid, adding anhydrous alcohol into separated liquid, separating out precipitate, washing with anhydrous alcohol, filtering to eliminate waste liquid to obtain wet glue, drying at room temperature for 12hr, and drying at 40 deg.c for 24hr to constant weight to obtain 7.3g epoxidized butadiene rubber.

Hydrolysis: dissolving 1g of the above prepared epoxidized butadiene rubber in 100ml of tetrahydrofuran, adding dropwise a solution prepared from 5ml of water and 1ml of perchloric acid at 25 ℃ under stirring, and stirring at 25 ℃ for 12hr after 30 min.¹HNMR (DMSO) analysis shows that the characteristic chemical shift peak of the epoxidized butadiene rubber disappears (the characteristic chemical shift delta of an epoxy group is 2.98, and the characteristic chemical shift delta of an o-dihydroxy is 4.18). The reaction solution was neutralized by adding sodium carbonate. Dropping 1000ml water into the reaction solution, precipitating, separating precipitate, soaking in 400ml water for 24hr, filtering to remove water, air drying the obtained polymer substance at room temperature for 24hr, and drying in vacuum oven at 40 deg.C to constant weight. 1.12g of a translucent solid was obtained. Molecular weight of the product

The molar content of the o-dihydroxy C4 units is 98%, and the Tg value is 56 ℃.

Preparation example 2

2g of the epoxidized butadiene rubber prepared above was dissolved in 200ml of freshly distilled tetrahydrofuran and then added to a 500ml stainless steel autoclave; add 0.4g Raney nickel (ethanol blanket, rinse 3 times with tetrahydrofuran before adding to the reactor); pressurizing the autoclave with nitrogen to 1MPa, releasing the pressure to normal pressure, and repeating the steps of pressurizing with nitrogen and releasing the pressure for 3 times. Introducing hydrogen gas at 50 ℃ while stirring, and pressurizing to 1 MPa. Keeping hydrogen pressure, stirring and reacting for 12 hr.¹HNMR test, epoxy groupThe degree of ring opening of the clusters is about 75% (mol).

The temperature of the reaction liquid is reduced to 0 ℃, and the pressure is released. The catalyst was filtered off. Filtering the reaction solution of the catalyst, dropwise adding a solution prepared from 5ml of water, 1ml of perchloric acid and 5ml of tetrahydrofuran, finishing dropwise adding for 30min, allowing the reaction temperature to rise to 25 ℃, and keeping the temperature and stirring for 12 hr.¹HNMR (DMSO) analysis shows that the characteristic chemical shift peak of the epoxidized butadiene rubber disappears. 0.37g of solid sodium carbonate was added to the reaction solution, and stirred for 2 hr. Adding water dropwise into the reaction solution to precipitate, soaking in water for 24hr, filtering to remove water, air drying the obtained polymer at room temperature for 24hr, and drying in vacuum oven at 40 deg.C to constant weight. 2.35g of a milky white solid was obtained. Number average molecular weight of 133000, molar content of ortho-dihydroxy C4 units of 24.7%, and Tg value of 66 ℃.

Preparation example 3

Styrene-butadiene rubber: a commercially available styrene-butadiene rubber block (styrene unit/butadiene unit (S/B) of Qilu petrochemical Co., Ltd.) 27/73, weight average molecular weight

) Cut into about 2mm colloidal particles.

Epoxidation: in a 1000ml three-necked flask equipped with a stirrer and a thermometer, 6g of the above styrene-butadiene rubber crumb and 550ml of toluene were charged. Dissolving in constant temperature water bath at room temperature, stirring, and introducing nitrogen for several minutes when the solution is completely dissolved into a viscous state. Heating to 40 deg.C, adding 3.0g formic acid, and dropwise adding 8.2g 30% hydrogen peroxide aqueous solution under stirring; the reaction is continued for about 5hr under heat preservation,¹HNMR(CDCl₃) And analyzing, and eliminating the double bond characteristic chemical shift peak. Neutralizing the reaction product with 10% sodium carbonate solution to pH 7, separating water phase, water washing, separating liquid, adding anhydrous alcohol into separated liquid, separating out precipitate, washing with anhydrous alcohol, filtering to eliminate waste liquid to obtain wet glue, drying at room temperature for 12hr, and drying at 40 deg.c for 24hr to constant weight to obtain 6.33g epoxidized styrene-butadiene rubber.

Hydrolysis: dissolving 1g of the prepared epoxidized styrene-butadiene rubber in 100ml of tetrahydrofuran, dropwise adding a solution prepared from 5ml of water and 1ml of perchloric acid at 25 ℃ while stirring, and after 30min of dropwise additionStirring at 25 deg.C for 12 hr.¹HNMR (DMSO) analysis, epoxy characteristic chemical shift peak disappeared. The reaction solution was neutralized by adding sodium carbonate. Dropping 1000ml water into the reaction solution, precipitating, separating precipitate, soaking in 500ml water for 24hr, filtering to remove water, air drying the obtained polymer substance at room temperature for 24hr, and drying in vacuum oven at 40 deg.C to constant weight. 1.1g of a white solid is obtained, the proportion of o-dihydroxyl C4 units being 62%.

Example 1

Preparation of glass bonding material:

respectively dissolving the product of preparation example 1, the product of preparation example 2, the product of preparation example 3 and PVB (polyvinyl butyral, a sample of which is purchased from New Youngen materials Co., Ltd., Changzhou, and is in a powder shape, the viscosity is less than 100cps, the acetalization degree is 68-78%) in dimethyl sulfoxide, adding an antioxidant 1010 according to 0.05% of the weight of a polymer to prepare a mixed glue solution with the weight of 50%, respectively pouring the solution into a mould, soaking in water to remove a solvent, then drying at 80 ℃ to constant weight, and respectively preparing films with the thickness of 0.8mm, namely the glass bonding material.

Glass adhesion test

4ml of each of the mixed solutions of 4 samples prepared in example 1 was uniformly spread on the surface of the glass in a 50mm (width) × 90mm (length) × 1.2mm (thickness) area. And sticking the fabric, wherein the specification of the fabric is 35mm multiplied by 85 mm. Soaking in water to remove solvent, and oven drying at 80 deg.C to constant weight.

The specification of the force measuring spring is phi 0.3 multiplied by 4 multiplied by 18 multiplied by 8N.

The evaluation method comprises the following steps: and measuring the original length of the spring in a standing state. The sticky cloth is hooked by the springs respectively, the sticky cloth is torn at an angle of 180 degrees, the length of the stretched springs is measured, and the stretching effects generated by 4 batches of samples are compared. The results are shown in Table 1.

TABLE 1 results of polymer glass adhesion test

From the experimental results, it can be seen that the adhesive materials comprising the polymers of preparation example 1, preparation example 2 and preparation example 3 have a stronger adhesion to glass than the adhesive materials comprising PVB.

Example 2

Preparation of polymer laminated glass:

(1) and preparing a film: the product of preparation example 1, the product of preparation example 2, the product of preparation example 3 and PVB were dissolved in dimethyl sulfoxide respectively, antioxidant 1010 was added in an amount of 0.05% by weight of the polymer to prepare 50 wt% solutions, the solutions were poured into molds respectively, and the molds were soaked in water to remove the solvent, and then dried at 80 ℃ to constant weight to prepare films having a thickness of 0.8mm respectively.

(2) Preparing laminated glass: a polymer-containing film obtained in step (1) was interposed between two sheets of glass 50 mm. times.90 mm. times.1.2 mm, and pressed at 135 ℃ for 30 minutes under a pressure of 1kg to prepare a polymer laminated glass.

Falling ball impact (impact resistance test) experiment of polymer laminated glass

The wide edges of two ends of the rectangular polymer laminated glass are clamped and fixed, and the middle of the glass is suspended 10mm away from the ground.

The falling ball was 2.35g of stainless steel ball. The steel balls impact from the top of the polymer laminated glass in a high free fall of 150 mm. The results are shown in Table 2.

TABLE 2 falling ball impact test of polymer laminated glass

From the test results, it can be seen that the impact resistance of laminated glass comprising the polymers of preparation examples 1,2 and 3 is better than that of PVB laminated glass.

Example 3

Comparative light transmittance test

The polymer laminated glass prepared in example 2 was measured for light transmittance using an ultraviolet-visible spectrophotometer. The results are shown in Table 3, where the laminated glass comprising the polymers of preparation examples 1,2 and 3 has the same optical transmission as PVB.

TABLE 3 light transmittance test results for Polymer laminated glass

Example 4

Test of moisture resistance of Polymer laminated glass

The polymer laminated glass prepared in example 2 was placed above a closed water bath at 50 ℃. + -. 2 ℃ and 50mm from the water surface, and the temperature and humidity in the closed water bath were maintained. After 120 hours, the glass was removed to compare the changes of the polymer laminated glass. The results are shown in table 4 and fig. 1.

TABLE 4 test results of the moisture resistance of polymer laminated glass

Example 5

Water absorption test of glass-bonded Material

The obtained polymer film containing preparation example 1, polymer film containing preparation example 2, polymer film containing preparation example 3 and PVB film were placed above a closed water bath (50 mm from the water surface) at 50 ℃. + -. 2 ℃ respectively, and the temperature and humidity in the closed water bath were maintained, according to the method in example 1. Weighing at different times, and recording to the accuracy of 0.0001 g. The results are shown in FIG. 2.

As can be seen from FIG. 2, after 24 hours, the water absorption of each film reached a saturation value, but the water absorption of the polymer films comprising preparation example 1, preparation example 2 and preparation example 3 was lower than that of the PVB film.

Example 6

A glass bonding material was prepared according to the method of example 1, except that: the filler is replaced by a plasticizer: triethylene glycol bis (2-ethylbutyrate), added in an amount of 5.5 wt% of the polymer. And a laminated glass was prepared as in example 2.

The falling ball impact test, the light transmittance comparative test, the moisture resistance test and the water absorption test of the laminated glass were measured in accordance with examples 2,3, 4 and 5.

And (3) testing results: the laminated glass was prepared by adding triethylene glycol di (2-ethylbutyrate) plasticizer in an amount of 5.5 wt% based on the weight of the polymer, and the test results were the same as those of the laminated glass containing the polymers of preparation examples 1-3 in example 2.

The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A glass bonding composition, characterized in that the composition comprises a polyhydroxy polymer and a filler, wherein the polyhydroxy polymer is 50-99.99 parts by weight, and the filler is 0.01-50 parts by weight;

the polyhydroxy polymer at least contains ortho-dihydroxy;

the polyhydroxy polymer comprises a structural unit shown in a formula (I) and optionally structural units shown in a formula (II), a formula (III) and a formula (IV):

formula (I)

Formula (II)

Formula (III)

Formula (IV)

a. b, c, d, e and f are independently integers of 0 or more, and a and e are not 0 at the same time, a is an integer of 50 to 20000 and/or e is an integer of 50 to 20000;

g is an integer of 1 or more;

a ', b', c ', d', e 'and f' are independent integers which are not less than 0 and are not 0 at the same time;

the filler is selected from at least one of a plasticizer, an antioxidant, an ultraviolet resistant absorber, a dispersant, a pigment and silica.

2. The glass bonding composition of claim 1, wherein the polyhydroxy polymer is a homopolymer, a random copolymer, or a block copolymer.

3. The glass bonding composition according to claim 1, wherein R is₁、R₂、R₃、R₄、R₅And R₆Same or different, independently from each other selected from H, C_1-4Alkyl, unsubstituted or optionally substituted by one, two or more R_aSubstituted C_6-10And (4) an aryl group.

4. The glass bonding composition according to claim 3, wherein R is₁、R₂、R₃、R₄、R₅And R₆Identical or different, independently of one another, from the group consisting of H, methyl, phenyl, tolyl.

5. The glass bonding composition according to claim 4, wherein R is₁、R₂、R₃、R₄、R₅And R₆Identical or different, independently of one another, from H, methyl.

6. The glass bonding composition according to claim 5, wherein R is₁、R₂、R₃、R₄、R₅And R₆And the same, is selected from H.

7. The glass bonding composition according to claim 1, wherein R is₁₉Selected from H, cyano, C_1-4Alkyl, unsubstituted or optionally substituted by one, two or more R_aSubstituted C_6-10An aryl group; each R_aSame or different from each otherThis is independently selected from C_1-12An alkyl group.

8. The glass bonding composition according to claim 7, wherein R is₁₉Selected from phenyl, tolyl, cyano.

9. The glass bonding composition according to claim 1, wherein R is₇、R₈、R₉、R₁₀、R₁₁And R₁₂Same or different, independently from each other selected from H, C_1-4Alkyl, unsubstituted or optionally substituted by one, two or more R_aSubstituted C_6-10And (4) an aryl group.

10. The glass bonding composition according to claim 9, wherein R is₇、R₈、R₉、R₁₀、R₁₁And R₁₂Identical or different, independently of one another, from the group consisting of H, methyl, phenyl, tolyl.

11. The glass bonding composition according to claim 10, wherein R is₇、R₈、R₉、R₁₀、R₁₁And R₁₂Identical or different, independently of one another, from H, methyl.

12. The glass bonding composition according to claim 11, wherein R is₇、R₈、R₉、R₁₀、R₁₁And R₁₂And the same, is selected from H.

13. The glass bonding composition according to claim 1, wherein R is₁₃、R₁₆、R₁₇And R₁₈Same or different, independently from each other selected from H, C_1-4Alkyl, unsubstituted or optionally substituted by one, two or more R_aSubstituted C_6-10And (4) an aryl group.

14. The glass bonding composition according to claim 13, wherein R is₁₃、R₁₆、R₁₇And R₁₈Identical or different, independently of one another, from the group consisting of H, methyl, phenyl, tolyl.

15. The glass bonding composition according to claim 14, wherein R is₁₃、R₁₆、R₁₇And R₁₈Identical or different, independently of one another, from H, methyl.

16. The glass bonding composition according to claim 15, wherein R is₁₃、R₁₆、R₁₇And R₁₈And the same, is selected from H.

17. The glass bonding composition according to any one of claims 1 to 16, wherein b is an integer between 0 and 2000, c is an integer between 0 and 2000, d is an integer between 0 and 2000, f is an integer between 0 and 2000;

g is an integer between 1 and 10000;

a 'is an integer of 0-20000, b' is an integer of 0-2000, c 'is an integer of 0-2000, d' is an integer of 0-2000, e 'is an integer of 0-10000, f' is an integer of 0-2000; a 'and e' are not 0 at the same time;

h is an integer between 0 and 2000, i is an integer between 0 and 2000, j is an integer between 0 and 2000, and k is an integer between 0 and 2000;

n' is an integer between 1 and 10.

18. The composition for bonding glass according to claim 17, wherein a is an integer of 50 to 7000.

19. The glass-bonding composition according to claim 18, wherein a is an integer between 50 and 3000.

20. The glass bonding composition according to claim 17, wherein n' is 1 or 2.

21. The glass-bonding composition of any of claims 1-16, wherein the plasticizer is selected from at least one of triethylene glycol di (2-ethylbutyrate), triethylene glycol diisooctanoate, dipentaerythritol, and ethylene glycol esters.

22. The glass bonding composition of any of claims 1-16, wherein the antioxidant is selected from basf 1010 and/or basf 168.

23. The glass-bonding composition of any of claims 1-16, wherein the anti-UV absorber is selected from at least one of UV-326 and UV-P.

24. The glass-bonding composition of any one of claims 1-16, wherein the dispersant is polymeric dispersant GR-5100H.

25. The glass bonding composition of any of claims 1-16, wherein the pigment is selected from phthalocyanine blue, phthalocyanine green, pink, carbon black, or permanent yellow.

26. The glass bonding composition of any of claims 1-16, wherein the silica is fumed silica.

27. The glass-bonding composition according to any one of claims 1 to 16, wherein the plasticizer is 0 to 50 parts, the antioxidant is 0 to 2 parts, the ultraviolet absorber is 0 to 2 parts, the dispersant is 0 to 8 parts, the pigment is 0 to 10 parts, and the silica is 0 to 10 parts, in parts by weight, and at least one of the plasticizer, the antioxidant, the ultraviolet absorber, the dispersant, the pigment, and the silica is not 0.

28. The composition for glass bonding according to any one of claims 1 to 16, wherein the polymer has any one of the structures represented by the following formulae (1) and (2):

formula (1)

Formula (2)

a, d, g have a range of values as set forth in claim 17.

29. The glass bonding composition of any of claims 1-16, wherein the polyhydroxy polymer has a molar content of ortho-dihydroxy polymer structural units in the range of 20-100%;

the number average molecular weight of the polyhydroxy polymer is 1-22 ten thousand.

30. A glass bonding material comprising the glass bonding composition of any one of claims 1-29.

31. The glass bonding material of claim 30, wherein the glass bonding material is in the form of a film or a bead.

32. A method for producing a glass bonding material according to claim 30 or 31, characterized in that the method comprises the steps of:

33. The method according to claim 32, wherein the organic solvent is at least one of dimethyl sulfoxide, acetic acid, and ethanol.

34. The production method according to claim 32, wherein the mass concentration of the mixed solution of the polyhydroxypolymer, the organic solvent and the filler is 1 to 90%.

35. The method of claim 32, wherein the drying temperature is 50-200 ℃.

36. Use of the glass bonding material of claim 30 or 31 in laminated glass.

37. A laminated glass comprising the glass binder material as claimed in claim 30 or 31.

38. A method for producing the laminated glass according to claim 37, characterized by comprising the steps of: the laminated glass is produced by adding the glass bonding material according to claim 30 or 31 between two sheets of glass, pressing at 25 to 150 ℃ for 5 to 40 minutes after pressing.