CN110914355A

CN110914355A - Resin composition

Info

Publication number: CN110914355A
Application number: CN201880046401.7A
Authority: CN
Inventors: S·莫蒂默; M·西蒙斯
Original assignee: Hexcel Composites Ltd
Current assignee: Hexcel Composites Ltd
Priority date: 2017-07-12
Filing date: 2018-07-11
Publication date: 2020-03-24
Also published as: EP3652244A1; WO2019011982A1; JP2020526645A; JP7217258B2

Abstract

The present invention relates to a curable polymeric resin composition comprising: a resin component, a curing agent system comprising at least one component in the form of an amine-based curing agent, and multi-stage polymeric particles. The polymer resin composition has a viscosity of less than 100mpa.s at a temperature of 110 ℃.

Description

Resin composition

Technical Field

The present invention relates to a liquid polymer composition comprising a resin component, a curing agent and a particle system.

In particular, the present invention relates to liquid polymer compositions, in particular liquid resin compositions comprising a curing agent and a particle system, which are useful as infusion resins.

More particularly, the present invention also relates to a process for preparing a liquid resin composition comprising a monomer, a curing agent and a multistage polymer.

Technical problem

Impact modifiers are widely used to improve the impact strength of polymer resin compositions with the aim of compensating their inherent brittleness or embrittlement, notch sensitivity and crack propagation occurring at ambient and especially sub-zero temperatures. Thus, impact modified polymers are polymeric materials whose impact resistance and toughness have been enhanced by the addition of phase domains of rubber materials.

This is typically achieved by incorporating tiny rubber particles into the polymer matrix that can absorb or dissipate the impact energy. One possibility is to introduce the rubber particles in the form of core-shell particles. These core-shell particles, which very often have a rubbery core and a polymeric shell, have the following advantages: a rubbery core of appropriate particle size to effectively toughen and a grafted shell to have adhesion and compatibility with the thermoplastic substrate.

The impact modifying properties are a function of the particle size of the particles (especially the particle size of the rubber portion of the particles) and their amount. For a given amount of added impact modifier particles, an optimum average particle size is required for maximum impact strength.

These primary impact modifier particles are typically added to the polymeric material in the form of powder particles. These powder particles are agglomerated primary impact modifier particles. During blending of the polymer resin composition with the powder particles, the primary impact modifier particles are distributed in the polymer resin, but their distribution is not sufficiently uniform, resulting in an undesirable increase in viscosity.

Although the particle size of the impact modifier particles is in the nanometer range, the agglomerated powder particles are in the micrometer range. The latter is much easier to handle.

For many polymers, thermoplastic or thermoset polymers, it is very difficult or nearly impossible to properly disperse these multistage polymers in the form of core-shell particles as an agglomerated dry powder. The ideal uniform dispersion of the core-shell particles is to have no agglomerates after dispersion in the matrix.

WO2014/013028 discloses impregnation processes for fibrous substrates, liquid (meth) acrylic syrup for use in the impregnation processes, polymerization processes thereof and structured articles obtained thereof. The syrup comprises (meth) acrylic monomers, (meth) acrylic polymers and optionally impact modifiers in the form of fine particles.

WO2014/135815 discloses viscous liquid (meth) acrylic syrup comprising mainly a methacrylic or acrylic component and an impact modifying additive for enhancing the impact strength of the thermoplastic material obtained after polymerization of the syrup. Impact modifying additives are based on elastic domains consisting of macromolecular blocks with flexible properties. Multistage polymers, especially in the form of core/shell particles, are not disclosed.

WO2014/135816 discloses viscous liquid (meth) acrylic syrup comprising mainly methacrylic or acrylic components and organic or inorganic fillers, which is intended to reduce the proportion of residual monomers after polymerization of the (meth) acrylic syrup. The organic filler is selected from crosslinked PMMA beads. Multistage polymers, especially in the form of core/shell particles, are not disclosed.

EP0985692 discloses improved MBS impact modifiers. The MBS impact modifier is a multistage polymer in the form of a core/shell polymer and a method for preparing the same by emulsion polymerization.

WO 2014062531 discloses a polymer comprising: a thermoset epoxy terminated oxazolidone ring containing polymer modified by b) core shell rubber particles, wherein at least 50% of the core shell rubber particles are prepared by a process comprising the steps of: I) performing emulsion polymerization of the monomers in an aqueous dispersion medium to form thermoplastic core shell rubber particles; II) agglomerating the thermoplastic core shell rubber particles to form a slurry; and III) dewatering the slurry to form dewatered particles, and IV) drying the dewatered particles to form dried particles.

None of the prior art documents discloses a liquid polymer composition as claimed herein or a process for obtaining it.

It is an object of the present invention to provide liquid polymer compositions comprising multistage polymers and/or to provide improvements or advantages in general.

It is still another object of the present invention to also provide a liquid curable polymer resin composition comprising a multistage polymer in which a multistage polymer useful for polymerization is uniformly dispersed.

It is another object of the present invention to avoid or significantly reduce agglomeration of multistage polymers in curable liquid polymer resin compositions, particularly but not exclusively liquid epoxy resin compositions.

It is still a further object to provide a process for preparing a liquid polymer composition comprising an epoxy component, a curing agent and a multistage polymer wherein the multistage polymer is uniformly dispersed.

Still a further object is the use of a composition comprising monomers, (meth) acrylic polymers for impact modifying a polymer.

According to the present invention, there is provided a composition, composite or part, method and use as defined in any one of the appended claims.

According to an embodiment of the present invention, there is provided a curable polymer resin composition including: a resin system comprising at least one resin component; a curing agent system comprising at least one component in the form of an amine-based curing agent; and a particle system comprising multistage polymeric particles, wherein the viscosity of the composition at a temperature of 110 ℃ is less than 100mpa.s, preferably less than 90mpa.s, more preferably less than 80 mpa.s.

The range of viscosity at a temperature of 110 ℃ is preferably from 1 to 100mpa.s, from 5 to 90mpa.s, or from 15 to 80mpa.s and/or combinations of the foregoing ranges.

In a further embodiment, the resin system includes an epoxy resin component having a functionality of at least 2, preferably a functionality of at least 4. In another embodiment, the amine-based curing agent is an aromatic amine comprising an alkylene bridged aromatic amine.

Preferably, the amine-based curing agent is methylenedianiline, preferably 4, 4-methylenedianiline.

In a preferred embodiment, the amine curing agent is selected from alkyl alkanol aniline, preferably methylene-bis (diethylaniline) (MDEA), 4-methylene-bis (isopropyl-6-methylaniline) (MMIPA), methylene-bis (chlorodiethylaniline) (MCDEA), or bis-methylethylaniline-bis (chlorodiethylaniline) (MMEACDEA). More preferably, the amine curing agent is a mixture of methylene-bis (diethylaniline) (MDEA) and 4, 4-methylenebis (isopropyl-6-methylaniline) (MMIPA) and the ratio of MDEA to MMIPA is 2: 1.

In a further embodiment, the curing agent system comprises an additional component in the form of an alkyl phenylenediamine. Preferably, the additional component comprises an alkylthio alkyl phenylenediamine, preferably a dialkylthio alkyl phenylenediamine. The curing agent system may comprise 10 to 50 wt% of a dialkylsulfanylalkylphenylenediamine, preferably 20 to 40 wt% of a dialkylsulfanylalkylphenylenediamine.

The dialkylsulfanylalkylphenylenediamine may have the formula

And/or

Wherein Y is an alkyl group containing 1 to 4 carbon atoms, X is hydrogen or an alkyl group containing 1 to 4 carbon atoms, and R' are alkyl or alkylthio groups, preferably alkyl or alkylthio groups containing 1 to 4 carbon atoms.

In a further embodiment, the dialkylsulfanylphenyldiamine is a mixture comprising

Preferably, the dialkylsulfanylalkylbenzene and the amine component are both liquids at room temperature.

In one embodiment, the methylenedianiline compound is liquid at 20 ℃ and has the formula

Wherein R is₁、R₂、R₃、R₄、R_1'、R_2'、R_3'And R_4'Independently selected from: hydrogen; c₁To C₆Alkoxy, preferably C₁To C₄Alkoxy, wherein the alkoxy may be linear or branched, such as methoxy, ethoxy, and isopropoxy; c₁To C₆Alkyl, preferably C₁To C₄Alkyl, wherein the alkyl may be linear or branched and optionally substituted, such as methyl, ethyl, isopropyl and trifluoromethyl; halogen; and wherein R₁、R₂、R₃、R₄、R_1'、R_2'、R_3'And R_4'Is at least one of C₁To C₆An alkyl group.

In another embodiment of the present invention, the resin system may comprise: a first resin component (a) comprising a glycidyl ether epoxy resin, a second resin component (b) comprising a naphthalene-based epoxy resin component, and an amine curing agent comprising an amino-phenylfluorene curing agent (c). Preferably, the epoxy resin components a) and b) comprise up to 33 wt% of the second resin component, based on the total weight of components (a) and (b).

In one embodiment of the invention, the epoxy resin components a) and b) comprise 5 to 33 wt% of the second resin component, preferably 7 to 32.5 wt% of the second resin component, more preferably 12 to 32 wt% of the second resin component, even more preferably 19 to 32 wt% of the second resin component, most preferably 20 up to but not including 33 wt% of the second resin component, and/or combinations of the foregoing ranges.

The composition has the following important advantages: providing a combination of a desired high wet Tg of at least 130 ℃ and excellent mechanical properties including high toughness and post impact Compression (CAI) strength; while also providing a suitably long tooling window to enable the manufacture of large composite parts.

In one embodiment, the resin composition has a wet Tg of at least 130 ℃, preferably at least 140 ℃, more preferably at least 150 ℃ when cured at 190 ℃ for 120 minutes. Dry and wet Tg were measured by Dynamic Mechanical Analysis (DMA) according to ASTM D7028. After soaking in water for 2 weeks at a temperature of 70 ℃, wet tests were performed on the samples.

In a further embodiment of the invention, the one or more mechanical properties of the neat cured resin composition are as follows:

critical strain energy release rate GIc in the range of 500 to 1000J/m²Preferably 700 to 1000J/m²Measured according to astm d5045-99(2007) e1, and/or combinations of the foregoing ranges;

-a critical stress intensity factor KIc in the range of 1.0 to 2.5MPa 0.5, preferably 1.4 to 2.0MPa 0.5, or 1.6 to 2.0MPa 0.5, measured according to ASTM D5045-99(2007) e1, and/or combinations of the foregoing ranges;

-a modulus G in the range of 3.0 to 3.8, preferably 3.2 to 3.6, or 3.0 to 3.8, or 3.3 to 3.5 and/or combinations of the aforementioned ranges, measured according to ASTM D790;

-a Tg onset temperature (dry process) in the range of 130 to 220 ℃, or of 150 to 200 ℃, or preferably of 170 ℃ to 190 ℃ and/or combinations of the aforementioned ranges;

-a Tg onset temperature (wet process) in the range of 100 to 180 ℃, or of 120 to 170 ℃, preferably of 130 to 160 ℃, or of 125 to 145 ℃ and/or combinations of the aforementioned ranges.

The second resin component may include at least one of: bisphenol-A (BPA) diglycidyl ether and/or bisphenol-F (BPF) diglycidyl ether and derivatives thereof.

In one embodiment, the second resin component is present in an amount equal to or greater than 10 weight percent, preferably equal to or greater than 15 weight percent, and more preferably equal to or greater than 20 weight percent.

The non-naphthalene component of the composition can be present in an amount ranging from 10 to 90 weight percent, preferably from 20 to 45 weight percent, more preferably from 65 to 80 weight percent, and/or combinations of the foregoing ranges, based on the total weight of the composition.

In one embodiment, the curing agent has the following formula

Wherein R is⁰Each independently selected from: hydrogen; and groups inert in the polymerization of epoxy group-containing compounds, which are preferredOptionally selected from halogen, straight and branched alkyl groups having 1 to 6 carbon atoms, phenyl, nitro, acetyl and trimethylsilyl;

each R is independently selected from hydrogen and straight and branched alkyl groups having 1 to 6 carbon atoms; and

R¹each independently selected from R, hydrogen, phenyl, and halogen.

The curing agent system includes one or more of the following curing agent components: bis (secondary aminophenyl) fluorenes, or mixtures of bis (secondary aminophenyl) fluorenes and (primary aminophenyl) (secondary aminophenyl) fluorenes. Preferably, the curing agent comprises one or more of the following curing agents: 9, 9-bis (4-aminophenyl) fluorene, 4-methyl-9, 9-bis (4-aminophenyl) fluorene, 4-chloro-9, 9-bis (4-aminophenyl) fluorene, 2-ethyl-9, 9-bis (4-aminophenyl) fluorene, 2-iodo-9, 9-bis (4-aminophenyl) fluorene, 3-bromo-9, 9-bis (4-aminophenyl) fluorene, 9- (4-methylaminophenyl) -9- (4-ethylaminophenyl) fluorene, 1-chloro-9, 9-bis (4-aminophenyl) fluorene, 2-methyl-9, 9-bis (4-aminophenyl) fluorene, 2, 6-dimethyl-9, 9-bis (4-aminophenyl) fluorene, 1, 5-dimethyl-9, 9-bis (4-aminophenyl) fluorene, 2-fluoro-9, 9-bis (4-aminophenyl) fluorene, 1,2,3,4,5,6,7, 8-octafluoro-9, 9-bis (4-aminophenyl) fluorene, 2, 7-dinitro-9, 9-bis (4-aminophenyl) fluorene, 2-chloro-4-methyl-9, 9-bis (4-aminophenyl) fluorene, 2, 7-dichloro-9, 9-bis (4-aminophenyl) fluorene, 2-acetyl-9, 9-bis (4-aminophenyl) fluorene, 2-methyl-9, 9-bis (4-methylaminophenyl) fluorene, 2-chloro-9, 9-bis (4-ethylaminophenyl) fluorene, or 2-tert-butyl-9, 9-bis (4-methylaminophenyl) fluorene, 9- (4-methylaminophenyl) -9- (4-aminophenyl) fluorene, 9, 9-bis (4-ethylaminophenyl) fluorene, 9- (4-ethylaminophenyl) -9- (4-aminophenyl) fluorene, 9, 9-bis (4-propylaminophenyl) fluorene, 9, 9-bis (4-isopropylaminophenyl) fluorene, 9, 9-bis (4-butylaminophenyl) fluorene, 9, 9-bis (3-methyl-4-methylaminophenyl) fluorene, 9, 9-bis (3-chloro-4-methylaminophenyl) fluorene, 9- (4-methylaminophenyl) -9- (4-ethylaminophenyl) fluorene, 4-methyl-9, 9-bis (4-methylaminophenyl) fluorene, or 4-chloro-9, 9-bis (4-methylaminophenyl) fluorene.

In one embodiment, the curing agent component comprises a sterically hindered bis (primary aminophenyl) fluorene. In a preferred embodiment, the curing agent is selected from: 9, 9-bis (3-methyl-4-aminophenyl) fluorene, 9, 9-bis (3-ethyl-4-aminophenyl) fluorene, 9, 9-bis (3-phenyl-4-aminophenyl) fluorene, 9, 9-bis (3, 5-dimethyl-4-methylaminophenyl) fluorene, 9, 9-bis (3, 5-dimethyl-4-aminophenyl) fluorene, 9- (3, 5-dimethyl-4-methylaminophenyl) -9- (3, 5-dimethyl-4-aminophenyl) fluorene, 9- (3, 5-diethyl-4-aminophenyl) -9- (3-methyl-4-aminophenyl) fluorene, 1, 5-dimethyl-9, 9-bis (3, 5-dimethyl-4-methylaminophenyl) fluorene, 9, 9-bis (3, 5-diisopropyl-4-aminophenyl) fluorene, 9, 9-bis (3-chloro-4-aminophenyl) fluorene, 9, 9-bis (3, 5-dichloro-4-aminophenyl) fluorene, 9, 9-bis (3, 5-diethyl-4-methylaminophenyl) fluorene, or 9, 9-bis (3, 5-diethyl-4-aminophenyl) fluorene and/or a combination of any of the foregoing curing agents.

In another embodiment, the curing agent component includes a halogen substituted amino-phenylfluorene curing agent.

In one embodiment of the invention, the particle system comprises multistage polymer particles.

In another embodiment, the particle system is comprised of multi-stage polymer particles.

In a further embodiment of the invention, the polymer particles have a multilayer structure formed from a multistage polymer, said multilayer structure comprising at least one layer (a) comprising a polymer (a1) having a glass transition temperature below 0 ℃ and another layer (B) comprising a polymer (B1) having a glass transition temperature above 30 ℃.

In another embodiment, the polymer (B1) has a glass transition temperature of at least 30 ℃ and forms an outer layer of polymer particles.

In a preferred embodiment, the polymer particles have a multilayer structure comprising at least one segment (a) comprising a polymer (a1) having a glass transition temperature below 0 ℃, at least one segment (B) comprising a polymer (B1) having a glass transition temperature above 30 ℃, and at least one segment (P1), the segment (P1) comprising a (meth) acrylic polymer (P1) having a glass transition temperature of 30 ℃ to 150 ℃.

The (meth) acrylic polymer (P1) may not be grafted to either of the polymers (a1) and (B1). Alternatively, the (meth) acrylic polymer (P1) may be grafted to one or both of the polymers (a1) and (B1).

In a further embodiment, the polymer (B1) has a glass transition temperature of at least 30 ℃ and forms an intermediate layer of polymer particles.

In another embodiment, stage (a) is a first stage, with stage (B) comprising polymer (B1) grafted onto stage (a) comprising polymer (a1) or another intermediate layer, the first stage being defined as stage (a) comprising polymer (a1) that was prepared prior to stage (B) comprising polymer (B1).

In a further embodiment, the particle system comprises a mixture of multi-stage particles in combination with different particles selected from methacrylic polymer (P1) particles, or monomer (M1) particles, or polymethacrylatebutadiene/styrene (MBS) particles.

The particulate system is present in an amount ranging from 0.1 to 15 weight percent, preferably from 0.5 to 13 weight percent, more preferably from 1.5 to 11 weight percent, even more preferably from 2 to 8 weight percent, and most preferably from 2.5 to 7.5 weight percent, and/or a combination of any of the foregoing ranges, based on the weight of the curable polymeric resin composition.

In a further embodiment, the weight average particle size based on the diameter of the particles is in the range of from 15nm to 900nm, preferably from 20nm to 800nm, more preferably from 25nm to 600nm, even more preferably from 30nm to 550nm, still more preferably from 40nm to 400nm, even more advantageously from 75nm to 350nm, advantageously from 80nm to 300nm and/or combinations of the aforementioned ranges.

In another embodiment, an adhesive comprising a polymer composition as described previously herein is provided. The polymer composition may comprise a filler. Suitable fillers may be selected from: microspheres, glass beads, microspheres, talc, and silica.

In a further embodiment there is provided a process for producing a fibre-reinforced composite material, wherein a fibre material is laid up in an enclosure, a curable epoxy resin composition according to any one of the preceding claims is drawn through the reinforcing fibre material at a temperature of from 80 to 130 ℃, and once the resin has been drawn through the reinforcing material, the temperature is raised to a temperature in the range of from 150 to 190 ℃.

Definition of

The term "polymer powder" as used herein refers to a polymer comprising powder particles in the range of at least 1 micrometer (μm) obtained by agglomeration of a primary polymer comprising particles in the nanometer range.

The term "system" as used herein refers to a single component, or a mixture of components. The term "resin system" as used herein refers to a single resin component, or a plurality of resin components or a mixture of resins. The term "curative system" as used herein refers to a single curative component, or a plurality of curative components or a mixture of a plurality of curatives. The term "particulate system" as used herein refers to a single particle, or a mixture of multiple particles.

The term "primary particles" as used herein refers to spherical polymers comprising particles in the nanometer range. Preferably, the primary particles have a weight average particle size of from 20nm to 800 nm.

The term "particle size" as used herein refers to the volume average diameter of particles that are considered to be spherical.

The term "copolymer" as used herein means a polymer composed of at least two different monomers.

The term "multistage polymer" as used herein refers to a polymer formed in a sequential manner by a multistage polymerization process. One preferred process is a multistage emulsion polymerization process wherein the first polymer is a first stage polymer and the second polymer is a second stage polymer, i.e., the second polymer is formed by emulsion polymerization in the presence of the first emulsion polymer.

The term "(meth) acrylic" as used herein refers to all kinds of acrylic and methacrylic monomers.

The term "(meth) acrylic polymer" as used herein means that the (meth) acrylic polymer substantially includes a polymer containing 50% by weight or more of (meth) acrylic monomers in the (meth) acrylic polymer.

The term "epoxy resin" as used herein is understood to mean any organic compound having at least two functional groups of oxirane type which can be polymerized by ring opening. Various examples of epoxy resins are described in this application.

The term "(meth) acrylic resin" as used herein is understood to mean an adhesive based on acrylic and methacrylic monomers.

The term "masterbatch" as used herein is understood to mean a composition comprising a high concentration of an additive in a carrier material. The additive is dispersed in the carrier material.

The term "impact modifier" as used herein is understood to be a material that, once incorporated into a polymeric material, increases the impact resistance and toughness of the polymeric material through phase domains of the rubbery material or rubbery polymer.

The term "rubber" as used herein refers to the thermodynamic state of a polymer above its glass transition temperature.

The term "rubbery polymer" as used herein refers to a polymer having a glass transition temperature (Tg) below 0 ℃.

The curable polymer composition of the present invention comprises: a resin system comprising at least one resin component. The resin component is preferably an epoxy resin component. The component may include one or more epoxy components or resins having a functionality of 2 (difunctional) or higher (trifunctional, tetrafunctional, etc.).

A suitable epoxy difunctional epoxy resin component for the resin component forming the polymer composition or matrix may be any suitable difunctional epoxy resin. It should be understood that this includes any suitable epoxy resin having two epoxy functional groups. The difunctional epoxy resin may be saturated, unsaturated, cycloaliphatic or heterocyclic. The difunctional epoxy resin may be used alone or in combination with the multifunctional epoxy resin to form the resin component. It is also possible to use a resin component comprising only a polyfunctional epoxy resin.

Difunctional epoxy resin components include, for example, those based on: diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol a (optionally brominated), glycidyl ether of phenol-aldehyde adducts, glycidyl ether of aliphatic diols, diglycidyl ether, diethylene glycol diglycidyl ether, Epikote, Epon, aromatic epoxy resins, epoxidized olefins, brominated resins, aromatic glycidyl amines, heterocyclic glycidyl imines (imides) and amides, glycidyl ethers, fluorinated epoxy resins, or any combination thereof. The difunctional epoxy resin is preferably selected from: diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol a, diglycidyl dihydroxy naphthalene, or any combination thereof. Most preferred are diglycidyl ethers of bisphenol F. Diglycidyl ethers of bisphenol F are commercially available from Huntsman Advanced Materials (Brewster, N.Y.) under the trade names Araldite GY281 and GY285 and from Ciba-Geigy (location) under the trade name LY 9703. The difunctional epoxy resin component may be used alone or in combination with other difunctional or multifunctional epoxy resins to form a resin system.

The resin system may include one or more epoxy resins having a functionality greater than 2. Preferred multifunctional epoxy resins are those that are trifunctional or tetrafunctional. The multifunctional epoxy resin may be a combination of a trifunctional epoxy resin and a multifunctional epoxy resin. The multifunctional epoxy resin may be saturated, unsaturated, cycloaliphatic, alicyclic or heterocyclic.

Suitable multifunctional epoxy resins include, for example, those based on: phenol and cresol epoxy novolacs, glycidyl ethers of phenol-formaldehyde adducts; glycidyl ethers of dialiphatic diols; a diglycidyl ether; diethylene glycol diglycidyl ether; an aromatic epoxy resin; dialiphatic triglycidyl ethers, aliphatic polyglycidyl ethers; an epoxidized olefin; a brominated resin; an aromatic glycidyl amine; heterocyclic glycidyl imines (imides) and amides; a glycidyl ether; a fluorinated epoxy resin, or any combination thereof.

Trifunctional epoxy resins are understood to have three epoxide groups which are substituted directly or indirectly in the para-or meta-position on the benzene ring of the compound backbone. Tetrafunctional epoxy resins are understood to have four epoxide groups which are substituted directly or indirectly in the meta or para position on the benzene ring of the compound backbone.

The phenyl ring may additionally be substituted with other suitable non-epoxy substituents. Suitable substituents include, for example, hydrogen, hydroxy, alkyl, alkenyl, alkynyl, alkoxy, aryl, aryloxy, aralkyloxy, aralkyl, halo, nitro, or cyano. Suitable non-epoxy substituents may be attached to the benzene ring in the para or ortho position, or in the meta position not occupied by the epoxy group. Suitable tetrafunctional epoxy resins include N, N, N ', N' -tetraglycidyl-m-xylylenediamine (commercially available under the name Tetrad-X from Mitsubishi Gas Chemical Company (Chiyoda-Ku, Tokyo, Japan), and Erisys GA-240 (from CVC Chemicals, Morrestown, N.J.)). Suitable trifunctional epoxy resins include, for example, those based on: phenol and cresol epoxy novolacs; glycidyl ethers of phenol-aldehyde adducts; an aromatic epoxy resin; a dialiphatic triglycidyl ether; aliphatic polyglycidyl ethers; an epoxidized olefin; brominated resins, aromatic glycidyl amines and glycidyl ethers; heterocyclic glycidyl imines (imides) and amides; a glycidyl ether; a fluorinated epoxy resin, or any combination thereof.

An exemplary trifunctional epoxy resin component is triglycidyl meta-aminophenol. Triglycidyl meta-aminophenol is commercially available from Huntsman Advanced Materials (Monthey, switzerland) under the trade name Araldite MY 0610. Another exemplary trifunctional epoxy resin is triglycidyl para-aminophenol. Triglycidyl p-aminophenol is commercially available from Huntsman Advanced Materials (Monthey, switzerland) under the trade name Araldite MY 0510.

Additional examples of suitable multifunctional epoxy resin components include, for example, N '-tetraglycidyl-4, 4' -diaminodiphenylmethane (TGDDM, commercially available as Araldite MY720 and MY721 from Huntsman Advanced Materials (Monthey, switzerland), or as ELM 434 from Sumitomo), triglycidyl ethers of p-aminophenols (commercially available as Araldite MY 0500 or MY0510 from Huntsman Advanced Materials), dicyclopentadiene based epoxy resins such as Tactix 556 (commercially available from Huntsman Advanced Materials), tris- (hydroxyphenyl), and methane based epoxy resins such as Tactix 742 (commercially available from Huntsman Advanced Materials). Other suitable multifunctional epoxies include DEN 438 (from Dow Chemicals, Midland, MI), DEN439 (from Dow Chemicals), Araldite ECN 1273 (from Huntsman Advanced Materials), and Araldite ECN1299 (from Huntsman Advanced Materials).

Preferred resin systems comprise difunctional epoxy resins, or trifunctional epoxy resins or tetrafunctional epoxy resins or mixtures of any of these components. Preferably, the difunctional epoxy resin component is present in an amount ranging from 12 wt% to 22 wt%, based on the total weight of the resin system. More preferably, the difunctional epoxy resin is present in an amount ranging from 15 wt% to 19 wt%, based on the total weight of the resin system. The trifunctional epoxy resin is present in an amount ranging from 15 wt% to 35 wt%, based on the total weight of the resin system. Preferably, the trifunctional epoxy resin is present in an amount ranging from 20 wt% to 30 wt%, based on the total weight of the resin system. More preferably, the trifunctional epoxy resin is present in an amount ranging from 24 wt% to 28 wt%, based on the total weight of the resin system. The tetrafunctional epoxy resin is present in an amount ranging from 5 wt% to 15 wt%, based on the total weight of the resin system. Preferably, the tetrafunctional epoxy resin is present in an amount ranging from 8 wt% to 12 wt%, based on the total weight of the resin system. More preferably, the tetrafunctional epoxy resin is present in an amount ranging from 9 wt% to 11 wt%, based on the total weight of the resin system. Combinations of various preferred ranges of these three types of epoxy resins can be used in the preferred resin component.

In the most preferred resin component, the only tetra-functional epoxy resin is present in an amount ranging from 47 wt% to 87 wt%, preferably from 55 wt% to 65 wt%, more preferably from 58 wt% to 67 wt%, based on the total weight of the curable composition.

The dynamic viscosity of the curable liquid composition according to the invention before curing at a temperature of 110 ℃ ranges from 0.1 to 200mPa s, preferably from 10 to 150mPa s, advantageously from 50 to 100mPa s. The viscosity of the liquid composition can be easily measured at 0 using a rheometer.1s^-1To 100s^-1Shear force measurement of (2). The dynamic viscosity was measured at 25 ℃. If shear thinning is present, then at 1s^-1The shear force of (c) measures the viscosity.

In one embodiment, the (meth) acrylic polymer (P1) has a mass average molecular weight Mw of less than 100000g/mol, preferably less than 90000g/mol, more preferably less than 80000 g/mol, still more preferably less than 70000g/mol, advantageously less than 60000g/mol, more advantageously less than 50000g/mol, still more advantageously less than 40000 g/mol. Preferred ranges of mass average molecular weight Mw are 10000 to 100000g/mol, preferably 20000 to 90000g/mol, 30000 to 70000g/mol, even more preferably 35000 to 60000g/mol, advantageously most preferably 40000 to 50000g/mol and/or combinations of the aforementioned ranges.

In a further embodiment, the (meth) acrylic polymer (P1) has a mass average molecular weight Mw of greater than 100000g/mol, preferably greater than 110000 g/mol, more preferably greater than 125000 g/mol, still more preferably greater than 140000 g/mol. Preferred ranges of mass-average molecular weight Mw are from 100000 to 1000000g/mol, preferably from 120000 to 190000g/mol, from 130000 to 170000g/mol, even more preferably from 135000 to 160000g/mol, advantageously most preferably from 140000 to 150000g/mol and/or combinations of the aforementioned ranges.

The (meth) acrylic polymer (P1) has a mass average molecular weight Mw higher than 2000 g/mol, preferably higher than 3000g/mol, more preferably higher than 4000g/mol, still more preferably higher than 5000g/mol, advantageously higher than 6000g/mol, more advantageously higher than 6500 g/mol, still more advantageously higher than 7000 g/mol, most advantageously higher than 10000 g/mol.

The mass average molecular weight Mw of the (meth) acrylic polymer (P1) is between 2000 g/mol and 100000g/mol, preferably between 3000g/mol and 90000g/mol, more preferably between 4000g/mol and 80000 g/mol, advantageously between 5000g/mol and 70000g/mol, more advantageously between 6000g/mol and 50000g/mol, most advantageously between 10000g/mol and 40000 g/mol.

Preferably, the (meth) acrylic polymer (P1) is a copolymer comprising a (meth) acrylic monomer. More preferably, (meth) propyleneThe acid-based polymer (P1) is a (meth) acrylic polymer. Even more preferably, the (meth) acrylic polymer (P1) comprises at least 50% by weight of a monomer selected from (meth) acrylic acid C₁To C₁₂Monomers of alkyl esters. Advantageously preferably, the (meth) acrylic polymer (P1) comprises at least 50% by weight of a monomer chosen from methacrylic acids C₁To C₄Alkyl esters and acrylic acid C₁To C₈Alkyl ester monomers and mixtures thereof.

Preferably, the glass transition temperature Tg of the (meth) acrylic polymer (P1) is from 30 ℃ to 150 ℃. The glass transition temperature of the (meth) acrylic polymer (P1) is more preferably from 40 ℃ to 150 ℃, advantageously from 45 ℃ to 150 ℃, more advantageously from 50 ℃ to 150 ℃.

Preferably, the polymer (meth) acrylic polymer (P1) is not crosslinked.

Preferably, the polymer (meth) acrylic polymer (P1) is not grafted to any other polymer or polymers.

The (meth) acrylic polymer (P1) may include: 50 to 100 wt% methyl methacrylate, preferably 80 to 100 wt% methyl methacrylate, still more preferably 80 to 99.8 wt% methyl methacrylate; and 0.2 to 20 weight percent of a C1 to C8 alkyl acrylate monomer. Advantageously, the C1 to C8 alkyl acrylate monomer is selected from methyl acrylate, ethyl acrylate or butyl acrylate.

In a second preferred embodiment, the (meth) acrylic polymer (P1) comprises 0 to 50 wt% of functional monomer. Preferably, the (meth) acrylic polymer (P1) comprises from 0 wt% to 30 wt%, more preferably from 1 wt% to 30 wt%, even more preferably from 2 wt% to 30 wt%, advantageously from 3 wt% to 30 wt%, more advantageously from 5 wt% to 30 wt%, most advantageously from 5 wt% to 30 wt% of functional monomer.

The functional monomer may be a (meth) acrylic monomer. The functional monomer has formula (1) or formula (2):

wherein in the formulae (1) and (2), R₁Are all selected from H or CH₃(ii) a And in formula (1), Y is O, R₅Is H or an aliphatic or aromatic group having at least one atom other than C or H; and in formula (2), Y is N, R₄And/or R₃Is H or an aliphatic or aromatic group.

Preferably, the functional monomer (1) or (2) is selected from: glycidyl (meth) acrylate, acrylic acid or methacrylic acid, amides derived from these acids, for example dimethylacrylamide, 2-methoxyethyl acrylate or methacrylate, optionally quaternized 2-aminoethyl acrylate or 2-aminoethyl methacrylate, acrylate or methacrylate monomers containing phosphonate or phosphate groups, alkylimidazolidone (meth) acrylates, polyethylene glycol (meth) acrylates. Preferably, the polyethylene glycol group of the polyethylene glycol (meth) acrylate has a molecular weight of 400g/mol to 10000 g/mol.

The multistage polymers according to the invention have at least two stages which differ in terms of the polymer composition.

The form of the multistage polymer is preferably a polymer particle regarded as a spherical particle. These particles are also referred to as core-shell particles. The first segment forms the core and the second segment or all subsequent segments form the corresponding shell. Such multistage polymers, also known as core/shell particles, are preferred.

With respect to the polymer particles according to the present invention, which are primary particles, the weight average particle size thereof is 15nm to 900 nm. Preferably, the weight average particle size (diameter) of the polymer is from 20nm to 800nm, more preferably from 25nm to 600nm, still more preferably from 30nm to 550nm, still more preferably from 35nm to 500nm, advantageously from 40nm to 400nm, even more advantageously from 75nm to 350nm, advantageously from 80nm to 300 nm. The primary polymer particles may be agglomerated to give a polymer powder comprising the multistage polymer or (meth) acrylic polymer (P1) and the multistage polymer.

The polymer particles are obtained by a multistage process, for example a process comprising two, three or more stages.

The polymer particles have a multilayer structure comprising at least one layer (a) and another layer (B), wherein layer (a) comprises a polymer (a1) having a glass transition temperature below 0 ℃ and layer (B) comprises a polymer (B1) having a glass transition temperature above 30 ℃.

In a first preferred embodiment, the polymer (B1) having a glass transition temperature of at least 30 ℃ is the outer layer of the polymer particles having a multilayer structure.

In a second preferred embodiment, the polymer having a glass transition temperature of at least 30 ℃ (B1) is an intermediate layer of polymer particles having a multilayer structure prior to contacting the multistage polymer with monomer (M1).

Preferably, stage (a) is the first stage, stage (B) comprising polymer (B1) being grafted onto stage (a) comprising polymer (a1) or onto another intermediate layer. The first stage represents that stage (a) comprising polymer (a1) is prepared before stage (B) comprising polymer (B1).

During the last stage of the multistage process, no further polymer (a1) having a glass transition temperature below 0 ℃ is prepared in layer (a). This means that the polymer (a1) is never present in the outer layer of the particle having a multilayer structure. The polymer (A1) in layer (A) having a glass transition temperature below 0 ℃ is in the core of the polymer particles or in one of the inner layers.

Preferably, the polymer (a1) having a glass transition temperature below 0 ℃ in layer (a) is prepared in a first stage of the multi-stage process forming the core of the polymer particles having a multi-layer structure and/or before the polymer (B1) having a glass transition temperature above 60 ℃. Preferably, the polymer (A1) has a glass transition temperature of less than-5 ℃, more preferably less than-15 ℃ and advantageously less than-25 ℃.

In a first preferred embodiment, the polymer (B1) having a glass transition temperature of more than 60 ℃ is prepared in the last stage of forming the outer layer of the polymer particles having a multilayer structure in a multistage process.

In a second preferred embodiment, the polymer (B1) having a glass transition temperature of at least 30 ℃ is an intermediate layer of polymer particles having a multilayer structure, prepared in a stage subsequent to the stage of forming the polymer (a1) of the multistage process.

There may be one or more further intermediate layers, obtained by one or more intermediate stages.

The glass transition temperature Tg of the corresponding polymer can be evaluated by dynamic methods such as thermodynamic analysis (thermomechanical analysis).

In order to obtain samples of the respective polymers (a1) and (B1), they were prepared separately and not by a multi-stage process for easier evaluation and measurement of the respective glass transition temperatures Tg of the respective polymers of the respective stages.

As for the polymer (a1), in the first embodiment, it is a (meth) acrylic polymer containing at least 50 wt% of a monomer derived from an alkyl acrylate.

More preferably, the polymer (a1) comprises one or more comonomers copolymerizable with the alkyl acrylate, as long as the polymer (a1) has a glass transition temperature of less than 0 ℃.

The one or more comonomers in polymer (a1) are preferably selected from (meth) acrylic monomers and/or vinyl monomers.

The (meth) acrylic monomer in the polymer (A1) includes a monomer selected from the group consisting of (meth) acrylic acid C₁To C₁₂Monomers of alkyl esters. Still more preferably, the (meth) acrylic comonomer in polymer (a1) comprises C1 to C4 alkyl methacrylate monomers and/or C1 to C8 alkyl acrylate monomers.

Most preferably, the acrylic or methacrylic comonomer of polymer (a1) is selected from the group consisting of methyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof, as long as polymer (a1) has a glass transition temperature of less than 0 ℃.

Preferably, the polymer (a1) is crosslinked. This means that the crosslinker is added to one or more other monomers. The crosslinking agent comprises at least two groups that can be polymerized.

In a particular embodiment, polymer (a1) is a homopolymer of butyl acrylate.

In another particular embodiment, the polymer (a1) is a copolymer of butyl acrylate and at least one crosslinking agent. The crosslinking agent comprises less than 5 wt% of the copolymer.

More preferably, the polymer of the first embodiment (A1) has a glass transition temperature Tg of from-100 ℃ to 0 ℃, even more preferably from-100 ℃ to-5 ℃, advantageously from-90 ℃ to-15 ℃, more advantageously from-90 ℃ to-25 ℃.

As for the polymer (a1), in the second embodiment, the polymer (a1) is a silicone rubber-based polymer. The silicone rubber is, for example, polydimethylsiloxane. More preferably, the polymer of the second embodiment (A1) has a glass transition temperature Tg of from-150 ℃ to 0 ℃, even more preferably from-145 ℃ to-5 ℃, advantageously from-140 ℃ to-15 ℃, more advantageously from-135 ℃ to-25 ℃.

With respect to the polymer (a1), in the third embodiment, the polymer (a1) having a glass transition temperature of less than 0 ℃ contains at least 50% by weight of a polymer unit derived from isoprene or butadiene, and the segment (a) is the innermost layer of the polymer particles having a multilayer structure. In other words, the segment (a) comprising the polymer (a1) is the core of the polymer particle.

For example, as regards the polymer of the core of the second embodiment (a1), mention may be made of isoprene homopolymers or butadiene homopolymers, isoprene-butadiene copolymers, copolymers of isoprene with up to 98% by weight of vinyl monomers, and copolymers of butadiene with up to 98% by weight of vinyl monomers. The vinyl monomer may be styrene, an alkylstyrene, acrylonitrile, an alkyl (meth) acrylate, or butadiene or isoprene. In one embodiment, the core is a butadiene homopolymer.

More preferably, the polymer of the third embodiment (A1) comprising at least 50 wt% of polymer units derived from isoprene or butadiene has a glass transition temperature Tg of from-100 ℃ to 0 ℃, even more preferably from-100 ℃ to-5 ℃, advantageously from-90 ℃ to-15 ℃, even more advantageously from-90 ℃ to-25 ℃.

As the polymer (B1), there can be mentioned homopolymers and copolymers containing a monomer having a double bond and/or a vinyl monomer. Preferably, the polymer (B1) is a (meth) acrylic polymer.

Preferably, the polymer (B1) contains at least 70% by weight of a monomer selected from the group consisting of (meth) acrylic acid C₁To C₁₂Monomers of alkyl esters. Even more preferably, the polymer (B1) contains at least 80% by weight of monomeric methacrylic acid C₁To C₄Alkyl esters and/or acrylic acid C₁To C₈An alkyl ester monomer.

The polymer (B1) may be crosslinked.

Most preferably, the acrylic or methacrylic monomer of polymer (B1) is selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof, as long as polymer (B1) has a glass transition temperature of at least 30 ℃.

Advantageously, the polymer (B1) comprises at least 50% by weight, more advantageously at least 60% by weight, even more advantageously at least 70% by weight, of monomer units derived from methyl methacrylate.

Preferably, the glass transition temperature Tg of the polymer (B1) is from 30 ℃ to 150 ℃. The glass transition temperature of the polymer (B1) is more preferably from 50 ℃ to 150 ℃, still more preferably from 70 ℃ to 150 ℃, advantageously from 90 ℃ to 150 ℃, more advantageously from 90 ℃ to 130 ℃.

In another embodiment, the multistage polymer as described above has an additional stage which is a (meth) acrylic polymer (P1). The primary polymer particles according to this embodiment of the invention have a multilayer structure comprising at least one segment (a) comprising a polymer (a1) having a glass transition temperature below 0 ℃, at least one segment (B) comprising a polymer (B1) having a glass transition temperature above 30 ℃, and at least one segment (P) comprising a (meth) acrylic polymer (P1) having a glass transition temperature of 30 ℃ to 150 ℃.

Preferably, the (meth) acrylic polymer (P1) is not grafted to either of polymer (a1) or (B1).

With respect to the process for preparing the multistage polymer according to the present invention, it comprises the steps of:

a) by monomers or monomer mixtures (A)_m) Is polymerized to obtain at least one layer (A) comprising a polymer (A1) having a glass transition temperature below 0 DEG C

b) By monomers or monomer mixtures (B)_m) Is polymerized to obtain a layer (B) comprising a polymer (B1) having a glass transition temperature of at least 30 DEG C

Monomer or monomer mixture (A)_m) And a monomer or monomer mixture (B)_m) Monomers selected from the monomers used for the previously given polymer (a1) and polymer (B1) according to composition.

Preferably, step a) is performed before step b). More preferably, if only two stages are present, step b) is carried out in the presence of the polymer (a1) obtained in step a).

Advantageously, the process for preparing the multistage polymer composition according to the invention is a multistage process comprising the following steps, one after the other:

a) by monomers or monomer mixtures (A)_m) Is polymerized to obtain a layer (A) comprising a polymer (A1) having a glass transition temperature below 0 DEG C

b) By monomers or monomer mixtures (B)_m) The emulsion polymerization of (a) is carried out to obtain a layer (B) comprising a polymer (B1) having a glass transition temperature of at least 30 ℃.

The corresponding monomer or monomer mixture (A) forming layer (A) and layer (B) comprising polymers (A1) and (B1), respectively_m) And (B)_m) And the characteristics of the corresponding polymers (a1) and (B1) are the same as defined previously.

The process for preparing a multistage polymer may comprise a further step in a further stage between steps a) and b).

The process for preparing a multistage polymer may also comprise a further step of a further stage preceding steps a) and b). The seeds can be used by passing the monomer or monomer mixture (A)_m) The emulsion polymerization of (a) is carried out to obtain a layer (a) comprising a polymer (a1) having a glass transition temperature below 0 ℃. The seeds are preferably glassA thermoplastic polymer having a transition temperature of at least 20 ℃.

The multistage polymer is obtained as an aqueous dispersion of polymer particles. The solids content of the dispersion is from 10 to 65% by weight.

As to the process for producing the (meth) acrylic polymer (P1) according to the present invention, it comprises reacting the corresponding (meth) acrylic monomer (P1)_m) And (3) a step of polymerization. Corresponding (meth) acrylic monomer (P1)_m) The same as defined previously for the (meth) acrylic polymer (P1) and the (meth) acrylic polymer of the two preferred embodiments (P1).

The (meth) acrylic homo-or copolymer (P1) can be prepared in a batch or semi-continuous process:

for a batch process, the mixture of monomers is introduced all at once just before or after introduction of one or part of the initiator system,

for the semi-continuous process, the monomer mixture is added in multiple portions or continuously in parallel to the initiator addition (the initiator is also added in multiple portions or continuously) during a defined addition period, which may be 30 to 500 minutes.

The method for producing the polymer composition comprising the (meth) acrylic polymer (P1) and the multistage polymer has two preferred embodiments.

In a first preferred embodiment of the process, the (meth) acrylic polymer (P1) is polymerized in the presence of a multistage polymer. The (meth) acrylic polymer (P1) was prepared as an additional stage of the multistage polymer.

In a second preferred embodiment of the process, the (meth) acrylic polymer (P1) is polymerized separately and mixed or blended with the multistage polymer.

As to the process for producing a polymer composition comprising a (meth) acrylic polymer (P1) and a multistage polymer, it comprises the following steps

a) By monomers or monomer mixtures (A)_m) Is polymerized to obtain a layer comprising a stage (A) of polymer (A1) having a glass transition temperature of less than 0 DEG C

b) Passing through sheetBody or monomer mixture (B)_m) Is polymerized to obtain a layer comprising stage (B) of polymer (B1) having a glass transition temperature of at least 30 DEG C

c) By monomers or monomer mixtures (P1)_m) Is polymerized to obtain a layer comprising the further stage of (meth) acrylic polymer (P1) having a glass transition temperature of at least 30 DEG C

Characterized in that the (meth) acrylic polymer (P1) has a mass-average molecular weight Mw of less than 100000 g/mol.

Preferably, step a) is performed before step b).

More preferably, step b) is carried out in the presence of the polymer (a1) obtained in step a).

Advantageously, the process for preparing a polymer composition comprising a (meth) acrylic polymer (P1) and a multistage polymer is a multistage process and comprises the following steps, one after the other:

b) By monomers or monomer mixtures (B)_m) Is polymerized to obtain a layer comprising stage (B) of polymer (B1) having a glass transition temperature of at least 30 DEG C

The respective monomers or monomer mixtures (A) of the layers (A), (B) and further stages, respectively, comprising the polymers (A1), (B1) and (P1), respectively, are formed_m)、(B_m) And (P1)_m) As defined previously. The characteristics of the polymers (a1), (B1) and (P1) respectively are the same as defined previously.

Preferably, the process for preparing a polymer composition comprising a (meth) acrylic polymer (P1) and a multistage polymer comprises the further step d) of recovering the multistage polymer composition.

Recovery means performing a partial separation between an aqueous phase and a solid phase, wherein the solid phase comprises a multi-stage polymer composition.

More preferably, according to the present invention, the recovery of the polymer composition is carried out by coagulation or by spray drying.

If the polymer (A1) having a glass transition temperature below 0 ℃ contains at least 50% by weight of polymer units derived from alkyl acrylates and stage (A) is the innermost layer of the polymer particles having a multilayer structure, spray drying is the preferred method for recycling and/or drying for the process for the preparation of the polymer powder composition according to the invention.

If the polymer (A1) having a glass transition temperature below 0 ℃ contains at least 50% by weight of polymer units derived from isoprene or butadiene and the block (A) is the innermost layer of polymer particles having a multilayer structure, coagulation is the preferred method for recovery and/or drying for the process for the preparation of the multistage polymer powder composition according to the invention.

The process for preparing the polymer composition according to the invention may optionally comprise a further step e) of drying the polymer composition.

Preferably, if step d) of recovering the polymer composition is carried out by coacervation, a drying step e) is carried out.

Preferably, after the drying step e), the multistage polymer composition comprises less than 3 wt.%, more preferably less than 1.5 wt.%, advantageously less than 1% of moisture or water.

The moisture content of the polymer composition can be measured with a thermobalance.

Drying of the polymer can be carried out in an oven or vacuum oven by heating the composition at 50 ℃ for 48 hours.

As to another method for producing a polymer composition comprising a (meth) acrylic polymer (P1) and a multistage polymer, it comprises the steps of:

a) mixing a (meth) acrylic polymer (P1) with a multistage polymer

b) Recovering the mixture obtained in the previous step in the form of a polymer powder

Wherein the (meth) acrylic polymer (P1) and the multistage polymer in step a) are in the form of a dispersion in an aqueous phase.

The amounts of the aqueous dispersion of (meth) acrylic polymer (P1) and of the aqueous dispersion of multistage polymer are chosen in such a way that the weight ratio of multistage polymer based solely on the solid fraction in the resulting mixture is at least 5 wt%, preferably at least 10 wt%, more preferably at least 20 wt%, advantageously at least 50 wt%.

The amounts of the aqueous dispersion of the (meth) acrylic polymer (P1) and the aqueous dispersion of the multistage polymer are selected in such a manner that the weight ratio of the multistage polymer based on only the solid portion in the resulting mixture is at most 99 wt%, preferably at most 95 wt%, more preferably at most 90 wt%.

The amounts of the aqueous dispersion of the (meth) acrylic polymer (P1) and the aqueous dispersion of the multistage polymer are selected in such a manner that the weight ratio of the multistage polymer based on only the solid portion in the resulting mixture is from 5 to 99% by weight, preferably from 10 to 95% by weight, more preferably from 20 to 90% by weight.

The recovery step b) of the process for preparing a polymer composition comprising the (meth) acrylic polymer (P1) and the multistage polymer is preferably carried out by coagulation or by spray drying.

The process for preparing a polymer composition comprising a (meth) acrylic polymer (P1) and a multistage polymer may optionally comprise a further step c) for drying the polymer composition.

Dry means that the polymer composition according to the invention comprises less than 3 wt% moisture, preferably less than 1.5 wt% moisture, more preferably less than 1.2 wt% moisture.

Humidity can be measured by a thermobalance that heats the polymer composition and measures weight loss.

The method of preparing the polymer composition comprising the (meth) acrylic polymer (P1) and the multistage polymer preferably produces a polymer powder. The polymer powder of the invention is in the form of granules. The polymer powder particles include agglomerated primary polymer particles prepared by a multistage process and a (meth) acrylic polymer (P1).

As for the polymer powder comprising the (meth) acrylic polymer (P1) and the multistage polymer according to two embodiments of the production method, it has a volume median particle size D50 of 1 μm to 500 μm. Preferably, the volume median particle size of the polymer powder is from 10 μm to 400 μm, more preferably from 15 μm to 350 μm, advantageously from 20 μm to 300 μm.

The volume particle size distribution D10 is at least 7 μm, preferably 10 μm.

The volume particle size distribution D90 is at most 950 μm, and preferably 500 μm, and most preferably at most 400 μm.

The weight ratio of the (meth) acrylic polymer (P1) to the multistage polymer is at least 5 wt%, more preferably at least 7 wt%, still more preferably at least 10 wt%.

According to the present invention, the weight ratio of the (meth) acrylic polymer (P1) to the multistage polymer is at most 95 w%.

Preferably, the weight ratio of the (meth) acrylic polymer (P1) to the multistage polymer is 5 to 95 wt%, preferably 10 to 90 wt%.

As regards the monomer (M1), it is a liquid monomer at least in the temperature range from 0 ℃ to 60 ℃. Monomer (M1) includes one C ═ C double bond.

The monomer (M1) according to the present invention is a monomer which is a solvent for the (meth) acrylic polymer (P1). In other words, the (meth) acrylic polymer (P1) is soluble in the monomer (M1).

Soluble means that within a certain time the (meth) acrylic polymer (P1) contacting the thermodynamically compatible monomer (M1) is dissolved and a solution of (meth) acrylic polymer (P1) in monomer (M1) is obtained.

The solubility of the (meth) acrylic polymer (P1) in the monomer (M1) can be tested simply by mixing the two compounds at 25 ℃ under agitation. For the person skilled in the art, the monomers (M1) comprising monomers as the majority of the polymerSolvents are known. On the other hand, the solubility parameter values are given for a large number of polymers and solvents, including a large number of monomers, such as those described in the following books: polymer Handbook (4)^thedition)Ed.J.Brandrup，E.H.Immergut and E.A.Grulke；Pub.:John Wiley and Sons Inc.1999，Chapter“Solubility Parameter Value”by Eric A.Gulke VII/675 to VII/714。

The monomer (M1) is preferably selected from (meth) acrylic and/or vinyl monomers and mixtures thereof. If the monomer (M1) is a mixture of several monomers, the (meth) acrylic polymer (P1) is soluble in the mixture comprising the monomer (M1).

The monomer (M1) is more preferably chosen from (meth) acrylic acid C₁To C₁₂Alkyl esters, styrenic monomers, and mixtures thereof.

The monomer (M1) may comprise at least 50% by weight of methyl methacrylate.

The monomer (M1) may be a monomer mixture comprising at least 50% by weight of methyl methacrylate, the balance making up 100% by weight being selected from the group consisting of C (meth) acrylic acid₂To C₁₂Alkyl esters, alkyl acrylates, styrenic monomers, and mixtures thereof.

The monomer (M1) may comprise at least 80% by weight of methyl methacrylate.

The monomer (M1) may be a monomer mixture comprising at least 80% by weight of methyl methacrylate, the balance making up 100% by weight being selected from the group consisting of C (meth) acrylic acid₂To C₁₂Alkyl esters, alkyl acrylates, styrenic monomers, and mixtures thereof.

The monomer (M1) may comprise at least 90% by weight of methyl methacrylate.

The monomer (M1) may be a monomer mixture comprising at least 90% by weight of methyl methacrylate, the balance making up 100% by weight being selected from the group consisting of C (meth) acrylic acid₂To C₁₂Alkyl esters, alkyl acrylates, styrenic monomers, and mixtures thereof.

The monomer (M1) may be methyl methacrylate alone.

Evaluation method

Viscosity measurement

Viscosity was measured using an MCR 301 rheometer from Anton Paar. A Couette geometry is used. The temperature was 25 ℃ and the shear rate was 0.1s^-1To 100s^-1。

Glass transition temperature

The glass transition temperature (Tg) of the polymer is measured with an instrument capable of performing thermodynamic analysis. RDAII "RHEOMETRICS DYNAMIC ANALYSER" proposed by Rheometrics Company has been used. Thermodynamic analysis accurately measures the viscoelastic changes of a sample as a function of applied temperature, strain or deformation. During the controlled program of temperature changes, the device continuously records the sample deformation, with the strain held fixed.

The results were obtained as follows: plots were made as a function of temperature, elastic modulus (G'), loss modulus and tan delta. Tg is the higher temperature value read in the tan delta curve when the derivative of tan delta is equal to 0.

Molecular weight

The mass average molecular weight (Mw) of the polymer was measured by Size Exclusion Chromatography (SEC).

Particle size analysis

The particle size of the primary particles after the multistage polymerization was measured with a Zetasizer.

The particle size of the polymer powder after recovery was measured using a MALVERN Mastersizer 3000 from MALVERN.

To estimate the weight average powder particle size, particle size distribution and ratio of the fine particles, a Malvern Mastersizer 3000 apparatus with a 300mm lens measuring the range of 0.5-880 μm was used.

GIc

GIc is the critical strain energy release rate, measured according to ASTM D5045-99(2007) e 1.

KIc

KIc is the critical stress intensity factor, which is determined according to ASTM D5045-99(2007) e 1.

Modulus of compression

The compressive modulus was measured on a pristine resin tube machined into parallel ends on an Instron mechanical testing machine using ASTM D790.

Dry E' Tg Dry and Wet Tg

Dry E' Tg dry and wet Tg were measured by Dynamic Mechanical Analysis (DMA) according to ASTM D7028. After soaking in water at a temperature of 70 ℃ for 2 weeks, wet tests were carried out on the samples.

Water absorption rate

The water absorption was determined by soaking a pre-weighed sample of neat resin (40mm x 8mm x 3mm) in water at a temperature of 70 ℃. Samples were taken after two weeks. Excess water was removed with a paper towel, the sample weighed, and then it was determined how much water had been absorbed.

The invention will now be elucidated by way of examples.

Examples

Synthesis of multistage polymer (core-shell particles) prepared according to the example of sample 1 of WO2012/038441, in order to obtain multistage polymer CS 1. It includes: a stage (A) comprising a polymer (A1) having a glass transition temperature below 0 ℃ (made substantially from butyl acrylate), and a stage (B) comprising a polymer (B1) having a glass transition temperature of at least 30 ℃ (made substantially from methyl methacrylate). The multistage polymer CS1 was kept as an aqueous dispersion for further use.

The synthesis of the (meth) acrylic polymer type (P1) was carried out according to two embodiments: in the first embodiment, the (meth) acrylic polymer (P1) is polymerized in the presence of the multistage polymer CS 1. The (meth) acrylic polymer (P1) was prepared as an additional stage of the multistage polymer CS. In the second embodiment, the (meth) acrylic polymer (P1) is separately polymerized and mixed or blended with the multistage polymer after the polymerization of the (meth) acrylic polymer (P1) is completed.

Particle 1 (comparative): the particles are multi-stage polymeric particles comprising a core of butyl acrylate (Tg of about-45 ℃) and a shell of polymethyl methacrylate (PMMA) (Tg >50 ℃). The particles are commercially available from arkema inc as Durastrength 480.

Particle 2: a (meth) acrylic polymer (P1) was prepared as an additional stage on the multistage polymer CS1 to form a multistage particle 2. Using a semi-continuous process: the reactor was charged with 6400g of multistage polymer in deionized water with stirring(CS1), 0.01g of FeSO₄And 0.032g of ethylenediaminetetraacetic acid sodium salt (dissolved in 10g of deionized water), 3.15g of sodium formaldehyde sulfoxylate dissolved in 110g of deionized water, and 21.33g of the emulsifier tallow fatty acid potassium salt (dissolved in 139.44g of water), the mixture being stirred until the added starting materials, excluding the core-shell polymer, are completely dissolved. Three vacuum-nitrogen purges were performed in succession, leaving the reactor under a slight vacuum. The reactor was then heated. At the same time, a mixture comprising 960.03g of methyl methacrylate, 106.67g of dimethylacrylamide and 10.67g of n-octyl mercaptan was degassed with nitrogen for 30 minutes. The reactor was heated at 63 ℃ and maintained at this temperature. Next, the monomer mixture was introduced into the reactor using a pump over 180 minutes. In parallel, a solution of 5.33g of tert-butyl hydroperoxide (dissolved in 100g of deionized water) was introduced (same addition time). The line was rinsed with 50g of water and 20g of water. The reaction mixture was then heated at a temperature of 80 ℃ and, after the end of the monomer addition, polymerization was carried out for 60 minutes until completion. The reactor was cooled to 30 ℃. The mass-average molecular weight of the (meth) acrylic polymer P1 was M_w＝28000g/mol。

The final polymer composition is then recovered and the polymer composition is dried by spray drying to obtain multi-stage particles 2.

Particle 3: the (meth) acrylic polymer (P1) was polymerized separately and mixed or blended with the multistage polymer CS 1. Synthesis of (meth) acrylic polymer (P1): semi-continuous process: into a reactor was charged 1700g of deionized water, 0.01g of FeSO under stirring₄And 0.032g of ethylenediaminetetraacetic acid sodium salt (dissolved in 10g of deionized water), 3.15g of sodium formaldehyde sulfoxylate dissolved in 110g of deionized water, and 21.33g of the emulsifier tallow fatty acid potassium salt (dissolved in 139.44g of water), the mixture being stirred until completely dissolved. Three vacuum-nitrogen purges were performed in succession, leaving the reactor under a slight vacuum. The reactor was then heated. At the same time, a mixture comprising 960.03g of methyl methacrylate, 106.67g of dimethylacrylamide and 10.67g of n-octyl mercaptan was degassed with nitrogen for 30 minutes. The reactor was heated at 63 ℃ and maintained at this temperature. Next, the monomer mixture was introduced into the reactor using a pump over 180 minutes. In parallel withA solution of 5.33g of tert-butyl hydroperoxide (dissolved in 100g of deionized water) was introduced (same addition time). The line was rinsed with 50g of water and 20g of water. The reaction mixture was then heated at a temperature of 80 ℃ and, after the end of the monomer addition, polymerization was carried out for 60 minutes until completion. The reactor was cooled to 30 ℃. The solids content obtained was 34.2%. The mass-average molecular weight of the (meth) acrylic polymer P1 was M_w＝28000g/mol。

The aqueous dispersion of the multistage polymer CS1 and the (meth) acrylic polymer (P1) were mixed in the following amounts: the weight ratio of (meth) acrylic polymer (P1) to multistage polymer CS1 was 15/85 based on solid polymer. The mixture was recovered as a powder by spray drying to give multi-stage granules 3.

Particle 4: the procedure of pellet 3 was repeated, but the weight ratio of (meth) acrylic polymer (P1) to multistage polymer CS1 was 25/75, based on solid polymer. In this way, after the mixture is recovered as powder by spray drying, the multistage particle 4 is obtained.

Particle 5 (comparative): the particles are commercially available multi-stage polymeric particles designated as MBS (polymethylmethacrylate butadiene/styrene) impact modifiers having a poly (butadiene/styrene) core and a polymethylmethacrylate shell. The granules are under the brand name

E950 sold by Arkema inc.

The performance of granule 1 and granule 3 were compared in a Resin Formulation (RF) comprising MY721 (supplied by Huntsman) and a curing agent system comprising two curing agent components in the form of methylene-bis (diethylaniline) (MDEA) and 4, 4-methylenebis (isopropyl-6-methylaniline) (MMIPA) with a ratio of MDEA to MMIPA of 2: 1. The curing agent system formed was 40 wt% based on the total weight of the resin component MY721 and the curing agent system.

Formulation RF was prepared as follows: granulate 1 and granulate 3 were blended into MY721 at different concentrations listed in the table below using a high speed mixer (Hauschild DAC 600FVZ) at a speed of 2,500rpm for 3 minutes. This process was repeated two more times, resulting in a total mixing time of 9 minutes.

From visual inspection of the dispersion, it can be seen that particles 1, regardless of concentration, are still present in the RF as agglomerates; regardless of the concentration of particles 3 in the RF, particles 3 are uniformly dispersed and no agglomerates are visible.

TABLE 1 neat resin mechanics data for RF containing particles 3

TABLE 2 Tg Properties of RF containing particles 3

TABLE 3 neat resin mechanics data for RF modified with particle 1

TABLE 4 Tg Properties of RF modified with particle 1

TABLE 5 viscosity at 110 ℃ of RF modified with particles 1 and RF modified with particles 3

The viscosity of the respective liquid compositions was measured. For comparable concentrations of multistage polymer particles, the viscosity of the RF modified with particle 1 is higher than the viscosity of the RF modified with particle 3.

The multi-segmented core-shell particles, particles 3, are more effectively dispersed and have a lower effective volume in the liquid epoxy resin composition.

At loadings of 5 wt%, 7.5 wt% and 10 wt%, based on the total weight of the formulation, particles 5 were dispersed in RF in the same manner as particles 1 and 3 described herein. No change in RF reactivity was observed. However, particles 5 were poorly dispersed in RF, and both visual observation and observation by electron microscopy indicated that particles 5 agglomerated. The toughness of the resin decreased, but no significant decrease in E' Tg (dry process) was found.

Poor dispersion of the particles 5 seems to influence the desired properties of the resin formulation RF.

Claims

1. A curable polymeric resin composition comprising

a. A resin system comprising at least one resin component,

b. a curing agent system comprising at least one component in the form of an amine-based curing agent, and

c. a particle system comprising a multi-stage polymer particle,

wherein the particles are present in an amount ranging from 2 to 10 wt%, preferably from 2 to 8 wt%, based on the weight of the curable polymer resin composition, and the composition has a viscosity ranging from 10 to 130mpa.s, preferably from 40 to 100mpa.s, at a temperature of 110 ℃.

2. The composition of claim 1, wherein the amine-based curing agent is an aromatic amine comprising a methylene bridged aromatic amine.

3. A composition according to any preceding claim, wherein the amine-based curing agent comprises methylenedianiline, preferably 4, 4-methylenedianiline.

4. The composition of claim 3, wherein the methylenedianiline is liquid at 20 ℃ and has the formula

Wherein R is₁、R₂、R₃、R₄、R_1'、R_2'、R_3'And R_4'Independently selected from:

hydrogen;

C₁to C₆Alkoxy, preferably C₁To C₄Alkoxy, wherein the alkoxy may be linear or branched, such as methoxy, ethoxy, and isopropoxy;

C₁to C₆Alkyl, preferably C₁To C₄Alkyl, wherein the alkyl may be linear or branched and optionally substituted, such as methyl, ethyl, isopropyl and trifluoromethyl;

halogen, such as chlorine;

wherein R is₁、R₂、R₃、R₄、R_1'、R_2'、R_3'And R_4'Is at least one of C₁To C₆An alkyl group.

5. The composition according to any one of the preceding claims, wherein the amine curing agent is selected from alkyl alkanol anilines, preferably methylene-bis (diethylaniline) (MDEA), 4-methylene bis (isopropyl-6-methylaniline) (MMIPA), methylene-bis (chlorodiethylaniline) (MCDEA), or dimethylethyl aniline-bis (chlorodiethylaniline) (MMEACDEA).

6. The composition of any of the preceding claims, wherein the amine curing agent is a mixture of methylene-bis (diethylaniline) (MDEA) and 4, 4-methylenebis (isopropyl-6-methylaniline) (MMIPA) and the ratio of MDEA to MMIPA is 2: 1.

7. The composition of claim 1 or 2, wherein the curing agent system comprises an alkyl phenylenediamine.

8. The composition of claim 6, wherein the alkyl phenylenediamine comprises a toluene diamine having one or more alkyl groups or one or more thioalkyl groups.

9. The composition of claim 6 or 7, wherein the alkyl phenylene diamine has the formula

And/or

10. The composition of claim 8, wherein the alkylphenylenediamine is present as a mixture and the ratio of structural component (i) to structural component (ii) is from 90:10 to 70:30, preferably 80: 20.

11. The composition of claim 8 or 9, wherein the curing agent system comprises 10 to 50 wt%, preferably 20 to 40 wt%, more preferably 18 to 25 wt% of a dialkylsulfanylphenyldiamine based on the weight of the curing agent system.

12. The composition of any one of claims 8 to 10, wherein the dialkylsulfanylphenyldiamine is a mixture comprising

13. The composition of any one of claims 7 to 10, wherein the dialkylsulfanylalkylbenzene and the amine component are both liquids at room temperature.

14. The composition of any preceding claim, wherein the amine-based curing agent is a mixture of two or more different alkylene-bridged aromatic amines.

15. The composition of claim 13, wherein the amine-based curing agent is a mixture selected from the group consisting of components comprising diphenylamine-based aromatic amines and alkylphenylenediamines.

16. The composition of claim 1, wherein the amine curing agent comprises an amino-phenylfluorene curing agent.

17. The composition of claim 1 or 2, wherein the curing agent has the following structural formula

Wherein R is⁰Each independently selected from: hydrogen; and groups inert in the polymerization of the epoxy group-containing compound, preferably selected from the group consisting of halogens, linear and branched alkyl groups having 1 to 6 carbon atoms, phenyl, nitro, acetyl and trimethylsilyl groups;

R¹each independently selected from R, hydrogen, phenyl, and halogen.

18. The composition of any one of claims 16 or 17, wherein the curing agent comprises a halogen substituted amino-phenylfluorene curing agent.

19. The composition of any one of claims 16 to 18, wherein the resin component is a mixture of at least a first resin polymer a) comprising a glycidyl ether epoxy resin and a second resin polymer b) comprising a naphthalene based epoxy resin, and wherein the epoxy resin polymers a) and b) comprise up to 33 wt% of the second resin polymer b), based on the total weight of polymers a) and b).

20. The composition of claim 23, wherein the second resinous polymer b) comprises at least one of: bisphenol-A (BPA) diglycidyl ether and/or bisphenol-F (BPF) diglycidyl ether and derivatives thereof.

21. The composition of any of claims 23 or 24, wherein the second resinous polymer b) is present in an amount equal to or greater than 10 wt.%, preferably in an amount equal to or greater than 15 wt.%, more preferably in an amount equal to or greater than 20 wt.%.

22. The composition of any one of claims 23 to 25, wherein the non-naphthalene component of the composition is present in an amount ranging from 10 to 90 wt%, preferably from 20 to 45 wt%, more preferably from 65 to 80 wt% and/or combinations of the foregoing ranges, based on the total weight of the composition.

23. The composition of any of the preceding claims wherein the polymer particles have a multilayer structure formed from multistage polymers, the multilayer structure comprising at least one layer (a) comprising a polymer (a1) having a glass transition temperature below 0 ℃ and another layer (B) comprising a polymer (B1) having a glass transition temperature above 30 ℃.

24. The composition of claim 15, wherein the polymer (B1) has a glass transition temperature of at least 30 ℃ and forms an outer layer of the polymer particles.

25. The composition of claim 16, wherein the polymer (B1) has a glass transition temperature of at least 30 ℃ and forms an intermediate layer of the polymer particles prior to contacting the multistage polymer with monomer (M1).

26. The composition of claim 17, wherein segment (a) is a first segment, segment (B) comprising polymer (B1) is grafted onto segment (a) comprising polymer (a1) or onto another intermediate layer, the first segment being defined as segment (a) comprising polymer (a1) that was prepared prior to segment (B) comprising polymer (B1).

27. The composition of any one of claims 16 to 19, wherein the polymer particles have a multilayer structure comprising at least one segment (a) comprising a polymer (a1) having a glass transition temperature below 0 ℃, at least one segment (B) comprising a polymer (B1) having a glass transition temperature above 30 ℃, and at least one segment (P1), the segment (P1) comprising a (meth) acrylic polymer (P1) having a glass transition temperature of 30 ℃ to 150 ℃.

28. The composition of claim 20, wherein (meth) acrylic polymer (P1) is not grafted to either of polymers (a1) and (B1).

29. The composition of claim 20, wherein (meth) acrylic polymer (P1) is grafted to one or both of polymers (a1) and (B1).

30. The composition according to any one of the preceding claims, wherein the weight average particle size based on the particle diameter is in the range of from 15nm to 900nm, preferably from 20nm to 800nm, more preferably from 25nm to 600nm, even more preferably from 30nm to 550nm, still more preferably from 40nm to 400nm, even more advantageously from 75nm to 350nm, and advantageously from 80nm to 300nm and/or combinations of the aforementioned ranges.

31. The composition of any of the preceding claims, wherein the resin component comprises an epoxy resin component having a functionality of at least 2, preferably a functionality of at least 4.

32. The composition of any of the preceding claims, wherein the resin component is an epoxy resin comprising N, N '-tetraglycidyl-4, 4' -diaminodiphenylmethane (TGDDM).

33. The composition of any preceding claim, wherein the multistage particles are present in an amount ranging from 0.1 to 15 wt.%, preferably from 0.5 to 13 wt.%, more preferably from 1.5 to 11 wt.%, even more preferably from 2 to 8 wt.%, most preferably from 2.5 to 7.5 wt.%, and/or a combination of any of the foregoing ranges, based on the weight of the curable polymer resin composition.

34. The composition according to any one of the preceding claims, wherein the particle system comprises a mixture of multi-stage particles in combination with different particles selected from methacrylic polymer (P1) particles, or monomer (M1) particles, or polymethacrylatebutadiene/styrene (MBS) particles.

35. The composition of any preceding claim, wherein the particulate system is present in an amount ranging from 0.1 to 15 wt%, preferably from 0.5 to 13 wt%, more preferably from 1.5 to 11 wt%, even more preferably from 2 to 8 wt%, most preferably from 2.5 to 7.5 wt%, and/or a combination of any of the foregoing ranges, based on the weight of the curable polymer resin composition.

36. The composition of any preceding claim, wherein the curative system is present in an amount ranging from 5 to 80 weight percent, preferably from 10 to 60 weight percent, more preferably from 15 to 50 weight percent, even more preferably from 18 to 42 weight percent, most preferably from 35 to 40 weight percent, and/or a combination of any of the foregoing ranges, based on the weight of the curable polymer resin composition.

37. The composition of any preceding claim, wherein the ratio of the resin component to the curative system is from 1:1 to 5:2, preferably from 2:1 to 4:3, more preferably 3: 2.

38. A composite or part comprising a fibrous reinforcement in combination with the composition of any preceding claim.

39. A process for preparing a fibre-reinforced composite material, wherein a fibre material is laid up in an enclosure and a curable epoxy resin composition according to any one of claims 1 to 25 is drawn through the reinforcing fibre material at a temperature of from 80 to 130 ℃, the temperature being raised to a temperature in the range of from 150 to 190 ℃ once the resin has been drawn through the reinforcing material.

40. Use of a composition according to any one of claims 1 to 28 as a curable resin in the production of a fibre-reinforced composite material.

41. Use according to claim 31 for producing a fibre-reinforced composite by the infusion method of claim 30.