CA2593606A1 - Impact-resistant compositions - Google Patents
Impact-resistant compositions Download PDFInfo
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- CA2593606A1 CA2593606A1 CA002593606A CA2593606A CA2593606A1 CA 2593606 A1 CA2593606 A1 CA 2593606A1 CA 002593606 A CA002593606 A CA 002593606A CA 2593606 A CA2593606 A CA 2593606A CA 2593606 A1 CA2593606 A1 CA 2593606A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
Abstract
The invention relates to compositions comprising at least one compound A, at least one linear or branched polyester B, and at least one toughening agent C, the linear or branched polyester B being produced from a macrocyclic poly(a,-alkylene-terephthalate) or a macrocyclic poly(a,-alkylene-2,6- naphtalene dicarboxylate) in the presence of an organotin catalyst or organotitanium catalyst). Also disclosed are a method for producing said compounds and the use thereof for producing composite members.
Description
IMPACT-RESISTANT COMPOSITIONS
Technical field The invention relates to the field of impact-resistant polyester compositions, in particular for use in fiber-reinforced composite products.
Prior art Thermoplastic polyesters are known plastics, and are widely used. Desirable properties for their use in fiber composites are not only good wetting of the fibers, i.e. low viscosity during production of a molding, but also high molecular weight, because of the mechanical properties required. However, the viscosity of the usual polyesters is too high for this application, particularly when the polyesters are used to produce moldings. US 5,498,651 discloses a polymerization process starting from low-viscosity macrocyclic polyester oligomers in the presence of polymerization catalysts and of epoxides and/or of thioepoxides. A particularly preferred epoxide disclosed for this application is 3,4-epoxycyclohexyl 3,4-epoxycyclohexanecarboxylate. US 6,197,849 describes organophilic phyllosilicates which are used as additive in thermosets (thermoset polymers), in particular in epoxy resins or in polyurethanes. US 5,707,439 describes the production of cation-exchanged lamellar minerals. Polymerization of macrocyclic oligomers in these cation-exchanged lamellar minerals is moreover revealed. However, polymer mixtures of this type are extremely difficult to process and lead to poor mechanical properties, since the lamellar minerals can act as nucleating agents.
Brief description of the invention It is therefore an object of the present invention to provide a composition which firstly has good processability and secondly has increased impact resistance.
The composition as claimed in claim 1 achieves this object.
Methods for carrying out the invention The present invention relates to compositions which encompass at least one compound A and also encompass at least one linear or branched polyester B, and also encompass at least one toughness improver C.
The compound A has at least two glycidyl ether groups and is preferably a diglycidyl ether of a bisphenol A
or of a bisphenol F, or of a bisphenol A/bisphenol F
mixture, or is a liquid oligomer thereof. Diglycidyl ethers of bisphenol A (DGEBA), of bisphenol F, and also of bisphenol A/F have proven to be particularly suitable compounds A (where the 'A/F' indicator here refers to a mixture which is composed of bisphenol A
and of bisphenol F and which is used as starting material in its preparation). By virtue of the preparation processes for these resins it is clear that there are also relatively high-molecular-weight constituents in the liquid resins. The structure of these diglycidyl ethers is shown by formula (I) . The degree of polymerization s in formula (I) for liquid resins is typically from 0.05 to 0.20. These liquid resins are available commercially, examples of typical commercial products being Araldite GY 250, Araldite PY 304, Araldite GY 282 (Huntsman), or D.E.R 331 ( Dow ) .
R R' R' Ra I I I I (I) ~--~ O L00 S O
\ / OH 0 Ra here is H or methyl.
Another possibility is that the compound A is a relatively high-molecular-weight solid epoxy resin of the formula (I) whose degree of polymerization s is typically from 2 to 12. There is, of course, always a distribution of molecular weights. Solid epoxy resins of this type are available commercially, for example from Dow or Huntsman or Resolution.
In one embodiment of the invention, a mixture of liquid epoxy resin and solid epoxy resin is used. The ratio by weight of liquid resin to solid resin is preferably from 9 : 1 to 1 : 1.
In particular, the polyester B is a linear polyester preferably having a structural formula (II) or (III).
O
e O"~
(II) m O
I O n~ * (III) Each of the indices n and n' here means 1, 2, 3, or 4.
In particular, n 1 or 3, and n' = 1 or 3. It is preferable that n 3 and n' = 3.
The indices m and m' have values from 50 to 2000, in particular from 50 to 800, preferably from 100 to 600, particularly preferably from 100 to 600.
Preferred polyesters B are poly(1,2-ethylene terephthalate) (PET), poly(1,2-ethylene 2,6-naphthale-nedicarboxylate) (PEN), and poly(1,4-butylene terephthalate) (PBT). The most preferred polyester B is poly(1,4-butylene terephthalate) (PBT).
The macrocyclic poly(a,(o-alkylene terephthalate) or macrocyclic poly(a,(o-alkylene 2,6-naphthalenedi-carboxylate) used for preparation of the polyester B
preferably has the structure of the formula (IV) R R' (IV) R' R p R here are an ethylene group, propylene group, butylene group, or pentylene group, and R' is a group of the formula O O
O-'"
0", e and R' O or O 0 O
The broken lines shown here are intended to indicate the bonds to the alkylene group R, and the index p has been selected so that the molar mass Mn of the macrocyclic poly(a,w-alkylene terephthalate) or of the macrocyclic poly(a,(o-alkylene 2,6-naphthalenedi-carboxylate) is from 300 to 2000 g/mol, in particular from 350 to 800 g/mol.
A known method, for example as described in the patent US 5,039,783, is used for preparation of the macrocyclic poly(a,w-alkylene terephthalate) or of the macrocyclic poly(a,(o-alkylene 2,6-naphthalenedi-carboxylate).
The organotin catalyst or organotitanium catalyst present in the preparation of the linear or branched polyester B is any catalyst known for this application to the person skilled in the art - for example known from US 5,407,984.
The amount of linear or branched polyester B in the composition is preferably from 85 to 98% by weight, with preference from 90 to 98% by weight, of the composition.
The composition moreover encompasses at least one toughness improver C. A "toughness improver" here and hereinafter is a material which is added to a matrix and which in particular in the case of thermosets, such as epoxy resins, brings about a marked increase in toughness when the amounts added are even as small as from 0.5 to 8% by weight, and which is therefore capable of absorbing a relatively high level of stress due to bending, tension, or impact before any cracking or breaking of the matrix occurs.
The toughness improver C is in particular an organic-ion-exchanged lamellar mineral Cl or a reactive liquid rubber C2, or a block copolymer C3.
The ion-exchanged lamellar mineral Cl can be either a cation-exchanged lamellar mineral Clc or an anion-exchanged lamellar mineral Cla.
The cation-exchanged lamellar mineral Cic is obtained here from a lamellar mineral C1' in which at least a portion of the cations has been exchanged for organic cations. Examples of these cation-exchanged lamellar minerals Clc are in particular those mentioned in US
5,707,439 or in US 6,197,849. That literature also describes the process for preparation of these cation-exchanged lamellar minerals Clc. A phyllosilicate is preferred as lamellar mineral C1'. The lamellar mineral Cl' is particularly preferably a phyllosilicate as described in US 6,197,849 column 2, line 38 to column 3, line 5, in particular a bentonite. Lamellar minerals Cl' such as kaolinite or a montmorillonite or a hectorite or an illite have proven particularly suitable.
At least a portion of the cations of the lamellar mineral C1' is exchanged for organic cations. These organic cations are in particular organic cations which have the formulae (V), (VI), (VII), (VIII), or (IX).
Each of the substituents R1, R", Rl", and R" is, independently of the others, H or C1-C20-alkyl, or substituted or unsubstituted aryl. It is preferable that Rl, R", Rlll , and R1"' are not the same substituent.
The substituent R 2 is H or C1-C20-alkyl, or substituted or unsubstituted aryl.
R' R~ N R(V) R
Rs R2 -N+ (VI) R4 ~R1 I l R2 R5 N+,O (VII) \
R
~
R6nN R' (VIII) R' N R' (IX) ~-j Each of the substituents R3 and R4 is H or Cl-C20-alkyl, or substituted or unsubstituted aryl, or an -N(R2)2 substituent. The substituent R5 is a substituent which, together with the N+ shown in formula (VII), forms an unsubstituted or substituted ring of from 4 to 9 atoms, and which, if appropriate, has double bonds. The substituent R6 is a substituent which, together with the N+ shown in formula (VIII), forms an unsubstituted or substituted bicyclic ring of from 6 to 12 atoms, and which, if appropriate, comprises heteroatoms, such as N, 0, and S, or their cations. The substituent R' is a substituent which, together with the N+ shown in formula (IX), forms an unsubstituted or substituted heteroaromatic ring whose size is from 5 to 7 atoms.
Specific examples of these organic cations of the formula (V) are n-octylammonium (R1 = n-octyl, R" = R1"
= R1"' = H) , trimethyldodecylammonium (Rl = C12-alkyl, R"
= R = R = CH3), dimethyldodecylammonium (Rl = C12-alkyl, Rl = Rlll = CH3r Rl- H), or bis(hydroxyethyl)octadecylammonium (R1 = C18-alkyl, R"
R1 = CH2CHZOH, R"" = H) , or similar derivatives of amines which can be obtained from natural fats and oils.
Specific examples of these organic cations of the formula (VI) are guanidinium cations or amidinium cations.
Specific examples of these organic cations of the formula (VII) are N-substituted derivatives of pyrrolidine, piperidine, piperazine, morpholine, thiomorpholine.
Specific examples of these organic cations of the formula (VIII) are cations of 1,4-diazobicyclo[2.2.2]octane (DABCO) and 1-azobicyclo[2.2.2]octane.
Specific examples of these organic cations of the formula (IX) are N-substituted derivatives of pyridine, pyrrole, imidazole, oxazole, pyrimidine, quinoline, isoquinoline, pyrazine, indole, benzimidazole, benzoxazole, thiazole, phenazine and 2,2'-bipyridine.
Further suitable cations are cyclic amidinium cations, in particular those disclosed in US 6,197,849 in column 3, line 6 to column 4, line 67.
Cyclic ammonium compounds feature increased thermal stability when compared with linear ammonium compounds, since they cannot undergo thermal Hoffmann degradation.
Preferred cation-exchanged lamellar minerals Cic are known to the person skilled in the art by the term organoclay or nanoclay, and are available commercially, for example with the product group names Tixogel , or NanofilU (SUdchemie), Cloisite (Southern Clay Products), or Nanomer (Nanocor Inc.).
The anion-exchanged lamellar mineral Cia is obtained here from a lamellar mineral Cl" in which at least a portion of the anions has been exchanged for organic anions. An example of an anion-exchanged lamellar mineral Cla of this type is a hydrotalcite in which at least a portion of the carbonate anions of the intermediate layers has been exchanged for organic anions.
It is certainly also possible that the composition simultaneously comprises a cation-exchanged lamellar mineral Cic and an anion-exchanged lamellar mineral C1a.
The reactive liquid rubber C2 has functional groups which at an elevated temperature, typically at a temperature of from 80 C to 200 C, in particular from 100 C to 160 C, can react with themselves or with other compounds in the composition. Particularly preferred functional groups of this type are epoxide groups.
Particular preference is given to the reactive liquid rubbers proposed for improving the toughness of epoxy resin adhesives. The reactive liquid rubber C2 is preferably a polyurethane prepolymer terminated by glycidyl ether groups. Reactive liquid rubbers C2 of the formula (X) have proven particularly suitable.
Technical field The invention relates to the field of impact-resistant polyester compositions, in particular for use in fiber-reinforced composite products.
Prior art Thermoplastic polyesters are known plastics, and are widely used. Desirable properties for their use in fiber composites are not only good wetting of the fibers, i.e. low viscosity during production of a molding, but also high molecular weight, because of the mechanical properties required. However, the viscosity of the usual polyesters is too high for this application, particularly when the polyesters are used to produce moldings. US 5,498,651 discloses a polymerization process starting from low-viscosity macrocyclic polyester oligomers in the presence of polymerization catalysts and of epoxides and/or of thioepoxides. A particularly preferred epoxide disclosed for this application is 3,4-epoxycyclohexyl 3,4-epoxycyclohexanecarboxylate. US 6,197,849 describes organophilic phyllosilicates which are used as additive in thermosets (thermoset polymers), in particular in epoxy resins or in polyurethanes. US 5,707,439 describes the production of cation-exchanged lamellar minerals. Polymerization of macrocyclic oligomers in these cation-exchanged lamellar minerals is moreover revealed. However, polymer mixtures of this type are extremely difficult to process and lead to poor mechanical properties, since the lamellar minerals can act as nucleating agents.
Brief description of the invention It is therefore an object of the present invention to provide a composition which firstly has good processability and secondly has increased impact resistance.
The composition as claimed in claim 1 achieves this object.
Methods for carrying out the invention The present invention relates to compositions which encompass at least one compound A and also encompass at least one linear or branched polyester B, and also encompass at least one toughness improver C.
The compound A has at least two glycidyl ether groups and is preferably a diglycidyl ether of a bisphenol A
or of a bisphenol F, or of a bisphenol A/bisphenol F
mixture, or is a liquid oligomer thereof. Diglycidyl ethers of bisphenol A (DGEBA), of bisphenol F, and also of bisphenol A/F have proven to be particularly suitable compounds A (where the 'A/F' indicator here refers to a mixture which is composed of bisphenol A
and of bisphenol F and which is used as starting material in its preparation). By virtue of the preparation processes for these resins it is clear that there are also relatively high-molecular-weight constituents in the liquid resins. The structure of these diglycidyl ethers is shown by formula (I) . The degree of polymerization s in formula (I) for liquid resins is typically from 0.05 to 0.20. These liquid resins are available commercially, examples of typical commercial products being Araldite GY 250, Araldite PY 304, Araldite GY 282 (Huntsman), or D.E.R 331 ( Dow ) .
R R' R' Ra I I I I (I) ~--~ O L00 S O
\ / OH 0 Ra here is H or methyl.
Another possibility is that the compound A is a relatively high-molecular-weight solid epoxy resin of the formula (I) whose degree of polymerization s is typically from 2 to 12. There is, of course, always a distribution of molecular weights. Solid epoxy resins of this type are available commercially, for example from Dow or Huntsman or Resolution.
In one embodiment of the invention, a mixture of liquid epoxy resin and solid epoxy resin is used. The ratio by weight of liquid resin to solid resin is preferably from 9 : 1 to 1 : 1.
In particular, the polyester B is a linear polyester preferably having a structural formula (II) or (III).
O
e O"~
(II) m O
I O n~ * (III) Each of the indices n and n' here means 1, 2, 3, or 4.
In particular, n 1 or 3, and n' = 1 or 3. It is preferable that n 3 and n' = 3.
The indices m and m' have values from 50 to 2000, in particular from 50 to 800, preferably from 100 to 600, particularly preferably from 100 to 600.
Preferred polyesters B are poly(1,2-ethylene terephthalate) (PET), poly(1,2-ethylene 2,6-naphthale-nedicarboxylate) (PEN), and poly(1,4-butylene terephthalate) (PBT). The most preferred polyester B is poly(1,4-butylene terephthalate) (PBT).
The macrocyclic poly(a,(o-alkylene terephthalate) or macrocyclic poly(a,(o-alkylene 2,6-naphthalenedi-carboxylate) used for preparation of the polyester B
preferably has the structure of the formula (IV) R R' (IV) R' R p R here are an ethylene group, propylene group, butylene group, or pentylene group, and R' is a group of the formula O O
O-'"
0", e and R' O or O 0 O
The broken lines shown here are intended to indicate the bonds to the alkylene group R, and the index p has been selected so that the molar mass Mn of the macrocyclic poly(a,w-alkylene terephthalate) or of the macrocyclic poly(a,(o-alkylene 2,6-naphthalenedi-carboxylate) is from 300 to 2000 g/mol, in particular from 350 to 800 g/mol.
A known method, for example as described in the patent US 5,039,783, is used for preparation of the macrocyclic poly(a,w-alkylene terephthalate) or of the macrocyclic poly(a,(o-alkylene 2,6-naphthalenedi-carboxylate).
The organotin catalyst or organotitanium catalyst present in the preparation of the linear or branched polyester B is any catalyst known for this application to the person skilled in the art - for example known from US 5,407,984.
The amount of linear or branched polyester B in the composition is preferably from 85 to 98% by weight, with preference from 90 to 98% by weight, of the composition.
The composition moreover encompasses at least one toughness improver C. A "toughness improver" here and hereinafter is a material which is added to a matrix and which in particular in the case of thermosets, such as epoxy resins, brings about a marked increase in toughness when the amounts added are even as small as from 0.5 to 8% by weight, and which is therefore capable of absorbing a relatively high level of stress due to bending, tension, or impact before any cracking or breaking of the matrix occurs.
The toughness improver C is in particular an organic-ion-exchanged lamellar mineral Cl or a reactive liquid rubber C2, or a block copolymer C3.
The ion-exchanged lamellar mineral Cl can be either a cation-exchanged lamellar mineral Clc or an anion-exchanged lamellar mineral Cla.
The cation-exchanged lamellar mineral Cic is obtained here from a lamellar mineral C1' in which at least a portion of the cations has been exchanged for organic cations. Examples of these cation-exchanged lamellar minerals Clc are in particular those mentioned in US
5,707,439 or in US 6,197,849. That literature also describes the process for preparation of these cation-exchanged lamellar minerals Clc. A phyllosilicate is preferred as lamellar mineral C1'. The lamellar mineral Cl' is particularly preferably a phyllosilicate as described in US 6,197,849 column 2, line 38 to column 3, line 5, in particular a bentonite. Lamellar minerals Cl' such as kaolinite or a montmorillonite or a hectorite or an illite have proven particularly suitable.
At least a portion of the cations of the lamellar mineral C1' is exchanged for organic cations. These organic cations are in particular organic cations which have the formulae (V), (VI), (VII), (VIII), or (IX).
Each of the substituents R1, R", Rl", and R" is, independently of the others, H or C1-C20-alkyl, or substituted or unsubstituted aryl. It is preferable that Rl, R", Rlll , and R1"' are not the same substituent.
The substituent R 2 is H or C1-C20-alkyl, or substituted or unsubstituted aryl.
R' R~ N R(V) R
Rs R2 -N+ (VI) R4 ~R1 I l R2 R5 N+,O (VII) \
R
~
R6nN R' (VIII) R' N R' (IX) ~-j Each of the substituents R3 and R4 is H or Cl-C20-alkyl, or substituted or unsubstituted aryl, or an -N(R2)2 substituent. The substituent R5 is a substituent which, together with the N+ shown in formula (VII), forms an unsubstituted or substituted ring of from 4 to 9 atoms, and which, if appropriate, has double bonds. The substituent R6 is a substituent which, together with the N+ shown in formula (VIII), forms an unsubstituted or substituted bicyclic ring of from 6 to 12 atoms, and which, if appropriate, comprises heteroatoms, such as N, 0, and S, or their cations. The substituent R' is a substituent which, together with the N+ shown in formula (IX), forms an unsubstituted or substituted heteroaromatic ring whose size is from 5 to 7 atoms.
Specific examples of these organic cations of the formula (V) are n-octylammonium (R1 = n-octyl, R" = R1"
= R1"' = H) , trimethyldodecylammonium (Rl = C12-alkyl, R"
= R = R = CH3), dimethyldodecylammonium (Rl = C12-alkyl, Rl = Rlll = CH3r Rl- H), or bis(hydroxyethyl)octadecylammonium (R1 = C18-alkyl, R"
R1 = CH2CHZOH, R"" = H) , or similar derivatives of amines which can be obtained from natural fats and oils.
Specific examples of these organic cations of the formula (VI) are guanidinium cations or amidinium cations.
Specific examples of these organic cations of the formula (VII) are N-substituted derivatives of pyrrolidine, piperidine, piperazine, morpholine, thiomorpholine.
Specific examples of these organic cations of the formula (VIII) are cations of 1,4-diazobicyclo[2.2.2]octane (DABCO) and 1-azobicyclo[2.2.2]octane.
Specific examples of these organic cations of the formula (IX) are N-substituted derivatives of pyridine, pyrrole, imidazole, oxazole, pyrimidine, quinoline, isoquinoline, pyrazine, indole, benzimidazole, benzoxazole, thiazole, phenazine and 2,2'-bipyridine.
Further suitable cations are cyclic amidinium cations, in particular those disclosed in US 6,197,849 in column 3, line 6 to column 4, line 67.
Cyclic ammonium compounds feature increased thermal stability when compared with linear ammonium compounds, since they cannot undergo thermal Hoffmann degradation.
Preferred cation-exchanged lamellar minerals Cic are known to the person skilled in the art by the term organoclay or nanoclay, and are available commercially, for example with the product group names Tixogel , or NanofilU (SUdchemie), Cloisite (Southern Clay Products), or Nanomer (Nanocor Inc.).
The anion-exchanged lamellar mineral Cia is obtained here from a lamellar mineral Cl" in which at least a portion of the anions has been exchanged for organic anions. An example of an anion-exchanged lamellar mineral Cla of this type is a hydrotalcite in which at least a portion of the carbonate anions of the intermediate layers has been exchanged for organic anions.
It is certainly also possible that the composition simultaneously comprises a cation-exchanged lamellar mineral Cic and an anion-exchanged lamellar mineral C1a.
The reactive liquid rubber C2 has functional groups which at an elevated temperature, typically at a temperature of from 80 C to 200 C, in particular from 100 C to 160 C, can react with themselves or with other compounds in the composition. Particularly preferred functional groups of this type are epoxide groups.
Particular preference is given to the reactive liquid rubbers proposed for improving the toughness of epoxy resin adhesives. The reactive liquid rubber C2 is preferably a polyurethane prepolymer terminated by glycidyl ether groups. Reactive liquid rubbers C2 of the formula (X) have proven particularly suitable.
g _ N O~ O
y1 y y2 r (X) O q In formula (X), Y1 is a q-valent radical of a linear or branched polyurethane prepolymer terminated by isocyanate groups, after removal of the terminal isocyanate groups, and Y2 is a radical of an aliphatic, cycloaliphatic, aromatic, or araliphatic epoxide comprising a primary or secondary hydroxy group, after removal of the hydroxide groups and epoxide groups. The index q here has a value of 2, 3, or 4, and the index r has a value of 1, 2, or 3. In one embodiment, the formula (X) has at least one aromatic structural element which has bonding by way of urethane groups to the polymer chain.
Liquid rubbers of the formula (XI) have proven to be particularly advantageous.
R,~/X\V N N O---y O v (XI) II y3 y 2 u O
In formula (XI), Y3 is a (u+w)-valent radical of a linear or branched polyurethane prepolymer terminated by isocyanate groups, after removal of the terminal isocyanate groups, and Y2 is a radical of an aliphatic, cycloaliphatic, aromatic, or araliphatic epoxide comprising a primary or secondary hydroxy group, after removal of the hydroxide groups and epoxide groups. The index w here has a value of 1, 2, or 3 and the index u has a value of 4 - w, and the index v has a value of 1, 2, or 3. In formula (XI), X is either 0 or NH or N-alkyl having from 1 to 6 carbon atoms, and R" is branched or unbranched alkyl or alkenyl substituents having from 6 to 24 carbon atoms, or a poly(dimethylsiloxane) radical whose molar mass is from 1000 to 10 000 g/mol. In one embodiment, the formula (XI) has at least one aromatic structural element which has bonding by way of urethane groups to the polymer chain.
The preparation of these reactive liquid rubbers takes place in the manner described by way of example in EP
1 431 325 Al, on page 4, line 37 to page 6, line 55.
Liquid rubbers C2 of the formulae (X) and (XI) can be used individually or preferably in a mixture. If they are used in a mixture, the ratio by weight of the liquid rubbers of the formulae (X) and (XI), (X)/(XI), is advantageously from 100:1 to 1:1.
The block copolymer C3 is obtained from anionic or controlled free-radical polymerization of methacrylic ester with at least one further monomer having an olefinic double bond. A monomer having an olefinic double bond is in particular one in which the double bond has direct conjugation with a heteroatom or with at least one further double bond. In particular, suitable monomers are those selected from the group consisting of styrene, butadiene, acrylonitrile, and vinyl acetate.
Particularly preferred block copolymers C3 are block copolymers composed of methyl methacrylate, styrene, and butadiene. These block copolymers are available, for example, in the form of triblock copolymers with the product group name SBM from Arkema.
In one embodiment, the toughness improver C present in the composition also comprises either a reactive liquid rubber C2 or a block copolymer C3 alongside an ion-exchanged lamellar mineral Cl. Particular preference is given to the simultaneous presence of ion-exchanged lamellar mineral C1 and of reactive liquid rubber C2. A
cation-exchanged lamellar mineral Clc is preferred here as ion-exchanged lamellar mineral Cl.
The amount of toughness improver C is preferably from to 85% by weight, based on the total weight of A +
C.
The composition can, if appropriate, have further 10 constituents, in particular fillers, plasticizers, agents with thixotropic effect, adhesion-promoter substances, in particular alkoxysilanes and titanates, stabilizers, in particular heat stabilizers, such as those known to the person skilled in the art as HALS
(Hindered Amine Light Stabilizers), and UV stabilizers, such as those available with trademark TINUVIN from Ciba Specialty Chemicals, or other additives familiar to the person skilled in the art in the formulation of adhesives, potting compositions, or sealing compositions. Compositions which comprise no solvents and/or plasticizers are preferred.
The compositions feature firstly high toughness and secondly good processing properties, for example low melt viscosity, while simultaneously featuring high melting point after polymerization.
The composition is preferably prepared via a process encompassing the following steps:
- formation of a premix AC of toughness improver C and of the compound A which has at least two glycidyl ether groups, - addition of the mixed premix AC to the macrocyclic poly(a,w-alkylene terephthalate) or macrocyclic poly(a,(o-alkylene 2,6-naphthalenedicarboxylate) which has been mixed with the organotin catalyst or organotitanium catalyst.
The linear or branched polyester B is preferably prepared at a temperature of from 160 C to 220 C, in particular from 160 C to 200 C, in the presence of the premix AC, and also of an organotin or organotitanium catalyst, via ring-opening polymerization, starting from a macrocyclic poly(a,w-alkylene terephthalate) or from a macrocyclic poly(a,(o-alkylene 2,6-naphthalenedicarboxylate).
The premix AC is preferably prepared via mixing to incorporate the toughness improver C into the compound A. This premixing preferably takes place at an elevated temperature with high shear forces. If the compound is a solid resin, the premix AC can also be prepared via mixing of compound A in powder form, or by means of extrusion.
It is preferable to begin by preparing a homogeneous premix of macrocyclic poly(a,(o-alkylene terephthalate) or of macrocyclic poly(a,co-alkylene 2,6-naphthalenedicarboxylate) and organotin catalyst or organotitanium catalyst at temperatures markedly below the polymerization temperature, e.g. in a twin-screw extruder, and then, after cooling, to grind the material to give a powder. The premix AC is then preferably added, with stirring, to a pulverulent premix of macrocyclic poly(a,(o-alkylene terephthalate) or macrocyclic poly(a,(o-alkylene 2,6-naphthalenedicarboxylate) and organotin or organotitanium catalyst at room temperature, and either charged in powder form to a mold or heated to the melting point of the macrocycle at from 160 to 180 C
and then charged in the form of liquid mixture to the mold. Ring-opening polymerization then takes place at temperatures above 180 C.
y1 y y2 r (X) O q In formula (X), Y1 is a q-valent radical of a linear or branched polyurethane prepolymer terminated by isocyanate groups, after removal of the terminal isocyanate groups, and Y2 is a radical of an aliphatic, cycloaliphatic, aromatic, or araliphatic epoxide comprising a primary or secondary hydroxy group, after removal of the hydroxide groups and epoxide groups. The index q here has a value of 2, 3, or 4, and the index r has a value of 1, 2, or 3. In one embodiment, the formula (X) has at least one aromatic structural element which has bonding by way of urethane groups to the polymer chain.
Liquid rubbers of the formula (XI) have proven to be particularly advantageous.
R,~/X\V N N O---y O v (XI) II y3 y 2 u O
In formula (XI), Y3 is a (u+w)-valent radical of a linear or branched polyurethane prepolymer terminated by isocyanate groups, after removal of the terminal isocyanate groups, and Y2 is a radical of an aliphatic, cycloaliphatic, aromatic, or araliphatic epoxide comprising a primary or secondary hydroxy group, after removal of the hydroxide groups and epoxide groups. The index w here has a value of 1, 2, or 3 and the index u has a value of 4 - w, and the index v has a value of 1, 2, or 3. In formula (XI), X is either 0 or NH or N-alkyl having from 1 to 6 carbon atoms, and R" is branched or unbranched alkyl or alkenyl substituents having from 6 to 24 carbon atoms, or a poly(dimethylsiloxane) radical whose molar mass is from 1000 to 10 000 g/mol. In one embodiment, the formula (XI) has at least one aromatic structural element which has bonding by way of urethane groups to the polymer chain.
The preparation of these reactive liquid rubbers takes place in the manner described by way of example in EP
1 431 325 Al, on page 4, line 37 to page 6, line 55.
Liquid rubbers C2 of the formulae (X) and (XI) can be used individually or preferably in a mixture. If they are used in a mixture, the ratio by weight of the liquid rubbers of the formulae (X) and (XI), (X)/(XI), is advantageously from 100:1 to 1:1.
The block copolymer C3 is obtained from anionic or controlled free-radical polymerization of methacrylic ester with at least one further monomer having an olefinic double bond. A monomer having an olefinic double bond is in particular one in which the double bond has direct conjugation with a heteroatom or with at least one further double bond. In particular, suitable monomers are those selected from the group consisting of styrene, butadiene, acrylonitrile, and vinyl acetate.
Particularly preferred block copolymers C3 are block copolymers composed of methyl methacrylate, styrene, and butadiene. These block copolymers are available, for example, in the form of triblock copolymers with the product group name SBM from Arkema.
In one embodiment, the toughness improver C present in the composition also comprises either a reactive liquid rubber C2 or a block copolymer C3 alongside an ion-exchanged lamellar mineral Cl. Particular preference is given to the simultaneous presence of ion-exchanged lamellar mineral C1 and of reactive liquid rubber C2. A
cation-exchanged lamellar mineral Clc is preferred here as ion-exchanged lamellar mineral Cl.
The amount of toughness improver C is preferably from to 85% by weight, based on the total weight of A +
C.
The composition can, if appropriate, have further 10 constituents, in particular fillers, plasticizers, agents with thixotropic effect, adhesion-promoter substances, in particular alkoxysilanes and titanates, stabilizers, in particular heat stabilizers, such as those known to the person skilled in the art as HALS
(Hindered Amine Light Stabilizers), and UV stabilizers, such as those available with trademark TINUVIN from Ciba Specialty Chemicals, or other additives familiar to the person skilled in the art in the formulation of adhesives, potting compositions, or sealing compositions. Compositions which comprise no solvents and/or plasticizers are preferred.
The compositions feature firstly high toughness and secondly good processing properties, for example low melt viscosity, while simultaneously featuring high melting point after polymerization.
The composition is preferably prepared via a process encompassing the following steps:
- formation of a premix AC of toughness improver C and of the compound A which has at least two glycidyl ether groups, - addition of the mixed premix AC to the macrocyclic poly(a,w-alkylene terephthalate) or macrocyclic poly(a,(o-alkylene 2,6-naphthalenedicarboxylate) which has been mixed with the organotin catalyst or organotitanium catalyst.
The linear or branched polyester B is preferably prepared at a temperature of from 160 C to 220 C, in particular from 160 C to 200 C, in the presence of the premix AC, and also of an organotin or organotitanium catalyst, via ring-opening polymerization, starting from a macrocyclic poly(a,w-alkylene terephthalate) or from a macrocyclic poly(a,(o-alkylene 2,6-naphthalenedicarboxylate).
The premix AC is preferably prepared via mixing to incorporate the toughness improver C into the compound A. This premixing preferably takes place at an elevated temperature with high shear forces. If the compound is a solid resin, the premix AC can also be prepared via mixing of compound A in powder form, or by means of extrusion.
It is preferable to begin by preparing a homogeneous premix of macrocyclic poly(a,(o-alkylene terephthalate) or of macrocyclic poly(a,co-alkylene 2,6-naphthalenedicarboxylate) and organotin catalyst or organotitanium catalyst at temperatures markedly below the polymerization temperature, e.g. in a twin-screw extruder, and then, after cooling, to grind the material to give a powder. The premix AC is then preferably added, with stirring, to a pulverulent premix of macrocyclic poly(a,(o-alkylene terephthalate) or macrocyclic poly(a,(o-alkylene 2,6-naphthalenedicarboxylate) and organotin or organotitanium catalyst at room temperature, and either charged in powder form to a mold or heated to the melting point of the macrocycle at from 160 to 180 C
and then charged in the form of liquid mixture to the mold. Ring-opening polymerization then takes place at temperatures above 180 C.
However, it is also possible to premix the mixture composed of AC, for example, in an extruder at temperatures below 140 C, and cool, grind, and store it, or else to cool the mixture prepared in the melt, and comminute and store it.
It is preferable that further use of the composition takes place before the final degree of polymerization is reached.
This type of preparation process has the advantage of permitting unexpectedly good and homogeneous incorporation of the toughness improver C, thus permitting use of solvents or plasticizer to be omitted or at least greatly reduced. A particular effect of this is to avoid unnecessary lowering of the melting point of the composition.
In one embodiment of the present invention, the composition described is used for production of composite products, in particular of nanocomposite materials (nanocomposites).
These composite products comprise at least one composition described above, and also fibers. The fibers are in turn fibers selected from the group consisting of glass fibers, metal fibers, carbon fibers, aramid fibers, mineral fibers, plant fibers, and mixtures thereof. Preferred fibers are carbon fibers or metal fibers. Steel fibers are particularly preferred. It is also possible that various types of fibers are simultaneously present in the composite product. The form in which the fibers are present can be that of short or long fibers, and specifically that of individual fibers or of rovings. Other forms in which the fibers can be present are that of knits, scrims, or wovens. The orientation of the fibers can be monodirectional or random. In one particularly preferred embodiment, the fibers present take the form of monodirectional fiber layers. It is also possible for a plurality of layers of these knits, scrims, or wovens to be present in a composite product. The fibers used, and the precise nature of orientation of the fibers, depend greatly on the geometry of the composite product and on the requirements placed upon the composite product in relation to mechanical loading.
The proportion of fibers in the composite product is preferably from 30 to 65% by volume, based on the volume of the composite product.
Various processes can be used in production of the composite product. For example, continuous profiles can be produced, in particular with sheet-like shape, by continuous unwinding from rolls of a plurality of rovings or of one or more fiber wovens, fiber scrims, or fiber knits, and drawing the fibers through a heated mold in which the molten composition is applied to the fibers, and penetrates the fibers. In one embodiment, the mold has an outlet through which the composite product is continuously discharged during cooling. In another embodiment, this mold likewise has an outlet through which the composite product is continuously discharged, but it is compacted in a further step downstream by means of presses, preferably heated presses, and, if necessary, converted to the desired cross-sectional geometry by means of a mask. In a cooling zone which follows, the composite product thus produced is cooled to room temperature. Finally, the continuous profile is rolled up or cut to length. These continuous profiles have particularly good suitability as reinforcement profiles, in particular as reinforcement sheets such as those used for the static reinforcement of construction works. These reinforcement profiles are advantageously bonded by means of adhesive to the structure requiring reinforcement, by a method which forces these two components together. Particularly preferred fibers which can be used for this are carbon fibers and glass fibers.
Composite products can moreover be filled with the composition by means of molds in which fibers are laid.
The final shape can be achieved by compression and forming. The processes used for this are very well known to the person skilled in the art and also include, in particular, RIM and RTM processes, inter alia.
Finally, especially when individual short fibers are used, the fibers can be homogeneously mixed with the molten composition, if appropriate during its preparation, and compressed or cast into a mold, in order to form a composite product.
The process used and the nature of the fiber reinforcement depend greatly on the requirements placed upon the composite product.
The inventive composite products are versatile. In particular, they are used for the static reinforcement of construction work or of a conveyance. They can either be used together with other materials or used alone. By way of example, mention may firstly be made of reinforcement of bridges, or of tunnels, or of buildings. Other examples are drivers' cabins, bodywork, bumpers, wheel surrounds, spare-wheel recesses, underbody and roof of automobiles, of rail vehicles, or of buses or trucks. Further examples of applications of these composite products are found in sports and leisure items, such as tennis rackets, bicycles, leisure boats. Preference is particularly given to any of the applications in which the use of these inventive composite products leads to a saving in weight when comparison is made with use of conventional materials.
Examples Com arative exam 1e 1(Ref. 1) :
It is preferable that further use of the composition takes place before the final degree of polymerization is reached.
This type of preparation process has the advantage of permitting unexpectedly good and homogeneous incorporation of the toughness improver C, thus permitting use of solvents or plasticizer to be omitted or at least greatly reduced. A particular effect of this is to avoid unnecessary lowering of the melting point of the composition.
In one embodiment of the present invention, the composition described is used for production of composite products, in particular of nanocomposite materials (nanocomposites).
These composite products comprise at least one composition described above, and also fibers. The fibers are in turn fibers selected from the group consisting of glass fibers, metal fibers, carbon fibers, aramid fibers, mineral fibers, plant fibers, and mixtures thereof. Preferred fibers are carbon fibers or metal fibers. Steel fibers are particularly preferred. It is also possible that various types of fibers are simultaneously present in the composite product. The form in which the fibers are present can be that of short or long fibers, and specifically that of individual fibers or of rovings. Other forms in which the fibers can be present are that of knits, scrims, or wovens. The orientation of the fibers can be monodirectional or random. In one particularly preferred embodiment, the fibers present take the form of monodirectional fiber layers. It is also possible for a plurality of layers of these knits, scrims, or wovens to be present in a composite product. The fibers used, and the precise nature of orientation of the fibers, depend greatly on the geometry of the composite product and on the requirements placed upon the composite product in relation to mechanical loading.
The proportion of fibers in the composite product is preferably from 30 to 65% by volume, based on the volume of the composite product.
Various processes can be used in production of the composite product. For example, continuous profiles can be produced, in particular with sheet-like shape, by continuous unwinding from rolls of a plurality of rovings or of one or more fiber wovens, fiber scrims, or fiber knits, and drawing the fibers through a heated mold in which the molten composition is applied to the fibers, and penetrates the fibers. In one embodiment, the mold has an outlet through which the composite product is continuously discharged during cooling. In another embodiment, this mold likewise has an outlet through which the composite product is continuously discharged, but it is compacted in a further step downstream by means of presses, preferably heated presses, and, if necessary, converted to the desired cross-sectional geometry by means of a mask. In a cooling zone which follows, the composite product thus produced is cooled to room temperature. Finally, the continuous profile is rolled up or cut to length. These continuous profiles have particularly good suitability as reinforcement profiles, in particular as reinforcement sheets such as those used for the static reinforcement of construction works. These reinforcement profiles are advantageously bonded by means of adhesive to the structure requiring reinforcement, by a method which forces these two components together. Particularly preferred fibers which can be used for this are carbon fibers and glass fibers.
Composite products can moreover be filled with the composition by means of molds in which fibers are laid.
The final shape can be achieved by compression and forming. The processes used for this are very well known to the person skilled in the art and also include, in particular, RIM and RTM processes, inter alia.
Finally, especially when individual short fibers are used, the fibers can be homogeneously mixed with the molten composition, if appropriate during its preparation, and compressed or cast into a mold, in order to form a composite product.
The process used and the nature of the fiber reinforcement depend greatly on the requirements placed upon the composite product.
The inventive composite products are versatile. In particular, they are used for the static reinforcement of construction work or of a conveyance. They can either be used together with other materials or used alone. By way of example, mention may firstly be made of reinforcement of bridges, or of tunnels, or of buildings. Other examples are drivers' cabins, bodywork, bumpers, wheel surrounds, spare-wheel recesses, underbody and roof of automobiles, of rail vehicles, or of buses or trucks. Further examples of applications of these composite products are found in sports and leisure items, such as tennis rackets, bicycles, leisure boats. Preference is particularly given to any of the applications in which the use of these inventive composite products leads to a saving in weight when comparison is made with use of conventional materials.
Examples Com arative exam 1e 1(Ref. 1) :
20 g of macrocyclic polybutylene terephthalate (PBT) are melted under nitrogen, with stirring at 160 C, with 1% of a titanate catalyst (PBT XB3 from Cyclics Corp.).
The melt is charged to a metal mold whose temperature is controlled to 195 C, where it is polymerized for 30 minutes with exclusion of air. This gives a sheet of dimensions 2*40*120 mm, from which test specimens are milled for subsequent mechanical tests.
Comparative examples 2 to 4 (Ref. 2, Ref. 3, Ref. 4) :
19.0 g of macrocyclic polybutylene terephthalate (PBT) are melted under nitrogen, with stirring at 160 C, with 1% of a titanate catalyst (PBT XB3 from Cyclics Corp.) and 1.0 g of liquid epoxy resin (Araldite GY 250, producer Huntsman). The melt is charged to a metal mold whose temperature is controlled to 195 C, where it is polymerized for 30 minutes with exclusion of air. This gives a sheet of dimensions 2*40*120 mm, from which test specimens are milled for subsequent mechanical tests (Ref. 2).
An analogous method is used for the experiments for Ref. 3 with 1.0 g of Araldite MY 790 (distilled, pure bisphenol A diglycidyl ether, producer Huntsman) and for Ref. 4 with 1.0 g of Araldite CY 179 (3,4-epoxycyclohexyl 3,4-epoxycyclohexanecarboxylate, producer Huntsman).
Corrm a ra t i ve exam 1 e 5 (Ref. 5) :
19.6 g of macrocyclic polybutylene terephthalate (PBT) are melted under nitrogen, with stirring at 175 C, with 1% of a titanate catalyst (PBT XB3 from Cyclics Corp.) and 0.4 g of Tixogel VZ (cation-exchanged bentonite, producer Sudchemie) is admixed. The resultant solution is charged for polymerization to a metal mold which is temperature-controlled to 195 C, where it is polymerized for 30 minutes with exclusion of air. This gives a sheet of dimensions 2*40*120 mm, from which test specimens are milled for subsequent mechanical tests.
Com pa ra t i ve example 6 (Ref. 6) :
Comparative example 6 (Ref. 6) is identical with Comparative example 5 (Ref. 5) except that twice the content of Tixogel VZ was used, i.e. 0.8 g for 19.2 g of PBT. However, it was found here that this high concentration of cation-exchanged lamellar mineral could not then be taken up homogeneously. No mechanical properties were therefore determined.
Inventive example 1 (1) :
g of SBM AF-X M22 (triblock copolymer composed of 15 styrene, butadiene, and methyl methacrylate in a ratio of 1:1:1, molecular weight 20 000 daltons, producer Arkema) ("SBM") are dissolved in 80 g of technical-grade bisphenol A diglycidyl ether (Araldite GY 250, Huntsman) under nitrogen, with stirring at 205 C. After 20 cooling to room temperature, a clear, highly viscous solution (AC) is obtained.
19.0 g of macrocyclic polybutylene terephthalate (PBT) are melted in an oil bath under nitrogen, with stirring at 175 C, with 1% of a titanate catalyst (PBT XB3 from Cyclics Corp.), and 1 g of the solution of SBM in liquid resin (AC) is admixed. The resultant solution is charged for polymerization to a metal mold which is temperature-controlled to 195 C, where it is polymerized for 30 minutes with exclusion of air. This gives a sheet of dimensions 2*40*120 mm, from which test specimens are milled for subsequent mechanical tests.
In ven t i ve example 2 (2) :
A reactive liquid rubber ("RLR") was prepared as follows:
200 g of PolyTHF 2000 (OH number 57.5 mg/g of KOH) were dried at 100 C in vacuo for 30 minutes. 47.5 g of IPDI and 0.04 g of dibutyltin dilaurate were then added. The reaction was conducted in vacuo at 90 C to constant NCO content of 3.58% after 2.5 h (theoretical NCO content: 3.700). 118.0 g of technical-grade trimethylolpropane glycidyl ether (Araldite DY-T, producer Huntsman, OH content 1.85 equivalents/kg) were then added. Stirring was continued at 90 C in vacuo until NCO content had fallen below 0.1%, after a further 3 h. This gave a clear product whose epoxy content was 2.50 eq/kg.
25 g of the resultant reactive liquid rubber (RLR1) are diluted with 75 g of technical-grade bisphenol A
diglycidyl ether (Araldite GY 250, Huntsman).
The melt is charged to a metal mold whose temperature is controlled to 195 C, where it is polymerized for 30 minutes with exclusion of air. This gives a sheet of dimensions 2*40*120 mm, from which test specimens are milled for subsequent mechanical tests.
Comparative examples 2 to 4 (Ref. 2, Ref. 3, Ref. 4) :
19.0 g of macrocyclic polybutylene terephthalate (PBT) are melted under nitrogen, with stirring at 160 C, with 1% of a titanate catalyst (PBT XB3 from Cyclics Corp.) and 1.0 g of liquid epoxy resin (Araldite GY 250, producer Huntsman). The melt is charged to a metal mold whose temperature is controlled to 195 C, where it is polymerized for 30 minutes with exclusion of air. This gives a sheet of dimensions 2*40*120 mm, from which test specimens are milled for subsequent mechanical tests (Ref. 2).
An analogous method is used for the experiments for Ref. 3 with 1.0 g of Araldite MY 790 (distilled, pure bisphenol A diglycidyl ether, producer Huntsman) and for Ref. 4 with 1.0 g of Araldite CY 179 (3,4-epoxycyclohexyl 3,4-epoxycyclohexanecarboxylate, producer Huntsman).
Corrm a ra t i ve exam 1 e 5 (Ref. 5) :
19.6 g of macrocyclic polybutylene terephthalate (PBT) are melted under nitrogen, with stirring at 175 C, with 1% of a titanate catalyst (PBT XB3 from Cyclics Corp.) and 0.4 g of Tixogel VZ (cation-exchanged bentonite, producer Sudchemie) is admixed. The resultant solution is charged for polymerization to a metal mold which is temperature-controlled to 195 C, where it is polymerized for 30 minutes with exclusion of air. This gives a sheet of dimensions 2*40*120 mm, from which test specimens are milled for subsequent mechanical tests.
Com pa ra t i ve example 6 (Ref. 6) :
Comparative example 6 (Ref. 6) is identical with Comparative example 5 (Ref. 5) except that twice the content of Tixogel VZ was used, i.e. 0.8 g for 19.2 g of PBT. However, it was found here that this high concentration of cation-exchanged lamellar mineral could not then be taken up homogeneously. No mechanical properties were therefore determined.
Inventive example 1 (1) :
g of SBM AF-X M22 (triblock copolymer composed of 15 styrene, butadiene, and methyl methacrylate in a ratio of 1:1:1, molecular weight 20 000 daltons, producer Arkema) ("SBM") are dissolved in 80 g of technical-grade bisphenol A diglycidyl ether (Araldite GY 250, Huntsman) under nitrogen, with stirring at 205 C. After 20 cooling to room temperature, a clear, highly viscous solution (AC) is obtained.
19.0 g of macrocyclic polybutylene terephthalate (PBT) are melted in an oil bath under nitrogen, with stirring at 175 C, with 1% of a titanate catalyst (PBT XB3 from Cyclics Corp.), and 1 g of the solution of SBM in liquid resin (AC) is admixed. The resultant solution is charged for polymerization to a metal mold which is temperature-controlled to 195 C, where it is polymerized for 30 minutes with exclusion of air. This gives a sheet of dimensions 2*40*120 mm, from which test specimens are milled for subsequent mechanical tests.
In ven t i ve example 2 (2) :
A reactive liquid rubber ("RLR") was prepared as follows:
200 g of PolyTHF 2000 (OH number 57.5 mg/g of KOH) were dried at 100 C in vacuo for 30 minutes. 47.5 g of IPDI and 0.04 g of dibutyltin dilaurate were then added. The reaction was conducted in vacuo at 90 C to constant NCO content of 3.58% after 2.5 h (theoretical NCO content: 3.700). 118.0 g of technical-grade trimethylolpropane glycidyl ether (Araldite DY-T, producer Huntsman, OH content 1.85 equivalents/kg) were then added. Stirring was continued at 90 C in vacuo until NCO content had fallen below 0.1%, after a further 3 h. This gave a clear product whose epoxy content was 2.50 eq/kg.
25 g of the resultant reactive liquid rubber (RLR1) are diluted with 75 g of technical-grade bisphenol A
diglycidyl ether (Araldite GY 250, Huntsman).
19.0 g of macrocyclic polybutylene terephthalate (PBT) are melted in an oil bath under nitrogen, with stirring at 175 C, with 1% of a titanate catalyst (PBT XB3 from Cyclics Corp.), and 1 g of the solution of RLR1 in liquid resin (AC) is admixed. The resultant solution is charged for polymerization to a metal mold which is temperature-controlled to 195 C, where it is polymerized for 30 minutes with exclusion of air.
In ven t i ve example 3 (3):
50 g of the reactive liquid rubber (RLR1) described in Inventive example 2 are diluted with 50 g of technical-grade bisphenol A diglycidyl ether (Araldite GY 250, Huntsman). 19.0 g of macrocyclic polybutylene terephthalate (PBT) are melted in an oil bath under nitrogen, with stirring at 175 C, with 1% of a titanate catalyst (PBT XB3 from Cyclics Corp.), and 1 g of the solution of RLR1 in liquid resin (AC) is admixed. The resultant solution is charged for polymerization to a metal mold which is temperature-controlled to 195 C, where it is polymerized for 30 minutes with exclusion of air.
In ven t i ve example 4 (4):
30 g of Cloisite 93A (cation-exchanged montmorillonite, producer Southern Clay Products) are stirred at 90 C with 70 g of technical-grade bisphenol A diglycidyl ether (Araldite GY 250, Huntsman). After one hour, the product is a clear viscous mass.
19.0 g of macrocyclic polybutylene terephthalate (PBT) are melted in an oil bath under nitrogen, with stirring at 160 C, with 1% of a titanate catalyst (PBT XB3 from Cyclics Corp.), and 1 g of the swollen phyllosilicate in liquid resin (AC) is admixed. The resultant solution is charged for polymerization to a metal mold which is temperature-controlled to 195 C, where it is polymerized for 30 minutes with exclusion of air.
In ven t i ve example 5 (5):
A reactive liquid rubber ("RLR") was prepared as follows:
An isocyanate-terminated prepolymer is prepared at 90 C
from 48.19 g (217 mmol) of isophorone diisocyanate (IPDI) and 200 g (100 mmol) of a,c0-dihydroxypolybutylene oxide (PolyTHF 2000, producer BASF) with 25 mg of dibutyltin dilaurate as catalyst.
11.1 g of monohydroxy-terminated poly(dimethylsiloxane) (Silaplan FM 041, molecular weight 1000 daltons, producer Itochu), and also 109 g of a technical-grade trimethylolpropane glycidyl ether (Araldite DY-T, producer Huntsman, OH content 1.85 equivalents/kg) were then added, with stirring. Isocyanate concentration is less than 0.1% after 60 minutes. The resultant reactive liquid rubber (RLR2) is diluted with 100 g of liquid epoxy resin (Araldite GY 250, producer Huntsman).
50 g of Cloisite 30B (cation-exchanged montmorillonite, producer Southern Clay Products) are admixed at 90 C with 150 g of this reactive liquid rubber diluted with liquid epoxy resin, and swollen to give a clear viscous paste. (AC) 19.0 g of macrocyclic polybutylene terephthalate (PBT) are melted in an oil bath under nitrogen, with stirring at 175 C, with 1% of a titanate catalyst (PBT XB3 from Cyclics Corp.), and 1 g of the RLR2/nanoclay/liquid resin premix (AC) described above is admixed. The resultant solution is charged for polymerization to a metal mold which is temperature-controlled to 195 C, where it is polymerized for 30 minutes with exclusion of air. This gives a sheet of dimensions 2*40*120 mm, from which test specimens are milled for subsequent mechanical tests.
Inventive example 6 (6) :
An isocyanate-terminated prepolymer is prepared at 90 C
from 48.19 g (217 mmol) of isophorone diisocyanate (IPDI) and 200 g (100 mmol) of a,w-dihydroxypolybutylene oxide (PolyTHF 2000, producer BASF) with 25 mg of dibutyltin dilaurate as catalyst.
The following are then added, with stirring: first 4.11 g (22.2 mmol) of n-dodecylamine, and then 109 g of a technical-grade trimethylolpropane glycidyl ether (Araldite DY-T, producer Huntsman, OH content 1.85 equivalents/kg). Isocyanate concentration is smaller than 0.1% after 60 minutes.
40 g of the resultant reactive liquid rubber (RLR3) are diluted with 40 g of technical-grade bisphenol A
diglycidyl ether (Araldite GY 250, Huntsman) and heated to 90 C, with stirring. 20 g of Cloisite 93A
(cation-exchanged montmorillonite, producer Southern Clay Products) are then added and swollen to give a clear viscous paste. (AC) 19.0 g of macrocyclic polybutylene terephthalate (PBT) are melted in an oil bath under nitrogen, with stirring at 175 C, with 1% of a titanate catalyst (PBT XB3 from Cyclics Corp.), and 1 g of the RLR3/nanoclay/liquid resin premix (AC) described above is admixed. The resultant solution is charged for polymerization to a metal mold which is temperature-controlled to 195 C, where it is polymerized for 30 minutes with exclusion of air.
In ven t i ve example 3 (3):
50 g of the reactive liquid rubber (RLR1) described in Inventive example 2 are diluted with 50 g of technical-grade bisphenol A diglycidyl ether (Araldite GY 250, Huntsman). 19.0 g of macrocyclic polybutylene terephthalate (PBT) are melted in an oil bath under nitrogen, with stirring at 175 C, with 1% of a titanate catalyst (PBT XB3 from Cyclics Corp.), and 1 g of the solution of RLR1 in liquid resin (AC) is admixed. The resultant solution is charged for polymerization to a metal mold which is temperature-controlled to 195 C, where it is polymerized for 30 minutes with exclusion of air.
In ven t i ve example 4 (4):
30 g of Cloisite 93A (cation-exchanged montmorillonite, producer Southern Clay Products) are stirred at 90 C with 70 g of technical-grade bisphenol A diglycidyl ether (Araldite GY 250, Huntsman). After one hour, the product is a clear viscous mass.
19.0 g of macrocyclic polybutylene terephthalate (PBT) are melted in an oil bath under nitrogen, with stirring at 160 C, with 1% of a titanate catalyst (PBT XB3 from Cyclics Corp.), and 1 g of the swollen phyllosilicate in liquid resin (AC) is admixed. The resultant solution is charged for polymerization to a metal mold which is temperature-controlled to 195 C, where it is polymerized for 30 minutes with exclusion of air.
In ven t i ve example 5 (5):
A reactive liquid rubber ("RLR") was prepared as follows:
An isocyanate-terminated prepolymer is prepared at 90 C
from 48.19 g (217 mmol) of isophorone diisocyanate (IPDI) and 200 g (100 mmol) of a,c0-dihydroxypolybutylene oxide (PolyTHF 2000, producer BASF) with 25 mg of dibutyltin dilaurate as catalyst.
11.1 g of monohydroxy-terminated poly(dimethylsiloxane) (Silaplan FM 041, molecular weight 1000 daltons, producer Itochu), and also 109 g of a technical-grade trimethylolpropane glycidyl ether (Araldite DY-T, producer Huntsman, OH content 1.85 equivalents/kg) were then added, with stirring. Isocyanate concentration is less than 0.1% after 60 minutes. The resultant reactive liquid rubber (RLR2) is diluted with 100 g of liquid epoxy resin (Araldite GY 250, producer Huntsman).
50 g of Cloisite 30B (cation-exchanged montmorillonite, producer Southern Clay Products) are admixed at 90 C with 150 g of this reactive liquid rubber diluted with liquid epoxy resin, and swollen to give a clear viscous paste. (AC) 19.0 g of macrocyclic polybutylene terephthalate (PBT) are melted in an oil bath under nitrogen, with stirring at 175 C, with 1% of a titanate catalyst (PBT XB3 from Cyclics Corp.), and 1 g of the RLR2/nanoclay/liquid resin premix (AC) described above is admixed. The resultant solution is charged for polymerization to a metal mold which is temperature-controlled to 195 C, where it is polymerized for 30 minutes with exclusion of air. This gives a sheet of dimensions 2*40*120 mm, from which test specimens are milled for subsequent mechanical tests.
Inventive example 6 (6) :
An isocyanate-terminated prepolymer is prepared at 90 C
from 48.19 g (217 mmol) of isophorone diisocyanate (IPDI) and 200 g (100 mmol) of a,w-dihydroxypolybutylene oxide (PolyTHF 2000, producer BASF) with 25 mg of dibutyltin dilaurate as catalyst.
The following are then added, with stirring: first 4.11 g (22.2 mmol) of n-dodecylamine, and then 109 g of a technical-grade trimethylolpropane glycidyl ether (Araldite DY-T, producer Huntsman, OH content 1.85 equivalents/kg). Isocyanate concentration is smaller than 0.1% after 60 minutes.
40 g of the resultant reactive liquid rubber (RLR3) are diluted with 40 g of technical-grade bisphenol A
diglycidyl ether (Araldite GY 250, Huntsman) and heated to 90 C, with stirring. 20 g of Cloisite 93A
(cation-exchanged montmorillonite, producer Southern Clay Products) are then added and swollen to give a clear viscous paste. (AC) 19.0 g of macrocyclic polybutylene terephthalate (PBT) are melted in an oil bath under nitrogen, with stirring at 175 C, with 1% of a titanate catalyst (PBT XB3 from Cyclics Corp.), and 1 g of the RLR3/nanoclay/liquid resin premix (AC) described above is admixed. The resultant solution is charged for polymerization to a metal mold which is temperature-controlled to 195 C, where it is polymerized for 30 minutes with exclusion of air.
Inventive example 7 (7) :
20 g of RLR3 (as described in Inventive example 6) are diluted with 60 g of technical-grade bisphenol A
diglycidyl ether (Araldite GY 250, Huntsman) and heated to 90 C, with stirring. 20 g of Cloisite 93A
(cation-exchanged montmorillonite, producer Southern Clay Products) are then added and swollen to give a clear viscous paste. (AC) 19.0 g of macrocyclic polybutylene terephthalate (PBT) are melted in an oil bath under nitrogen, with stirring at 175 C, with 1% of a titanate catalyst (PBT XB3 from Cyclics Corp.), and 1 g of the RLR3/nanoclay/liquid resin premix (AC) described above is admixed. The resultant solution is charged for polymerization to a metal mold which is temperature-controlled to 195 C, where it is polymerized for 30 minutes with exclusion of air.
Compa ra t i ve example 7 (Ref. 7) :
Comparative example 7 (Ref. 7) is identical with Inventive example 1 (1) except that an identical amount of Araldite CY 179 (3,4-epoxycyclohexyl 3,4-epoxycyclohexanecarboxylate, producer Huntsman) was used instead of Araldite GY 250. The test specimens thus produced were so brittle that they broke apart during milling and could not be tested.
20 g of RLR3 (as described in Inventive example 6) are diluted with 60 g of technical-grade bisphenol A
diglycidyl ether (Araldite GY 250, Huntsman) and heated to 90 C, with stirring. 20 g of Cloisite 93A
(cation-exchanged montmorillonite, producer Southern Clay Products) are then added and swollen to give a clear viscous paste. (AC) 19.0 g of macrocyclic polybutylene terephthalate (PBT) are melted in an oil bath under nitrogen, with stirring at 175 C, with 1% of a titanate catalyst (PBT XB3 from Cyclics Corp.), and 1 g of the RLR3/nanoclay/liquid resin premix (AC) described above is admixed. The resultant solution is charged for polymerization to a metal mold which is temperature-controlled to 195 C, where it is polymerized for 30 minutes with exclusion of air.
Compa ra t i ve example 7 (Ref. 7) :
Comparative example 7 (Ref. 7) is identical with Inventive example 1 (1) except that an identical amount of Araldite CY 179 (3,4-epoxycyclohexyl 3,4-epoxycyclohexanecarboxylate, producer Huntsman) was used instead of Araldite GY 250. The test specimens thus produced were so brittle that they broke apart during milling and could not be tested.
A C C/(A+C) Additive for PBT (B) [o]* [o]* [%]
Ref.1 -Ref.2 GY 250 (A) 5 Ref.3 MY 790 (A) 5 Ref.4 CY 179 (-) Ref.5 Tixogel0 VZ(C1) 2 100 Ref.6 Tixogel0 VZ (C1) 4 100 CY 179 (-) Ref.7 1 SBM (C3) GY 250 (A) 1 SBM (C3) 4 1 20 GY 250 (A) 2 3.75 1.25 25 RLR1 (C2) GY 250 (A) 3 2.5 2.5 50 RLR1 (C2) GY 250 (A) 4 3.5 1.5 30 Cloisite0 93A (Cl) GY 250 (A) Cloisite0 30 B(C1) 0.8 4.2 84 RLR2 (C2) GY 250 (A) 6 Cloisite0 93A (Cl) 2 3 60 RLR3 (C2) GY 250 (A) 7 Cloisite0 93A (Cl) 3 2 40 RLR3 (C2) Table 1: Composition of examples.
* based on the weight of the composition Test methods Flexural strength, flexural strain, and flexural modulus were measured to DIN EN ISO 178 (determination of flexural properties) on a 1185-5500R Instron tester at 2 mm/min at 23 C, 50% rel. humidity.
Flexural Flexural strain Flexural modulus strength [MPa] [o] [MPa]
Ref.1 51.0 1.6 3175 Ref.2 62.7 2.6 2704 Ref.3 55.8 2.0 2772 Ref.4 14.0 0.5 2614 Ref.5 25.87 0.8 2795 Ref.6 n.m.** n.m.** n.m.**
Ref.7 n.m.** n.m.** n.m.**
1 73.5 3.3 2684 2 77.41 4.65 2267 3 64.58 3.55 2024 4 85.82 4.5 2519 5 86.9 4.1 2709 6 81.73 4.38 2458 7 79.86 3.79 2395 Table 2: Mechanical properties of examples.
n.m. = not measurable Table 2 shows that formulations with technical-grade liquid epoxy resin (Araldite GY 250) which has a proportion of hydroxy-functional oligomers (s > 0 in formula (I)) exhibit better mechanical properties than those exhibited when using bisphenol A diglycidyl ether having no hydroxy groups (Araldite MY 790) (Ref. 2 and Ref. 3). Table 2 moreover shows that when compounds having two glycidyl ether groups, Araldite GY 250 and Araldite MY 790, are compared with Araldite CY 179 (3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane-carboxylate Ref. 4), there is a pronounced improvement in mechanical properties.
The results from the inventive compositions moreover show greatly increased values for mechanical properties. It is also noticeable that the inventive compositions simultaneously exhibit higher values for flexural strength and for flexural strain when compared with the comparative examples.
In the inventive compositions it is possible to achieve higher contents of toughness improvers than in the comparative examples. For example, mixing to achieve homogeneous incorporation using toughness improver content of 4% by weight in compositions is impossible to achieve Ref. 6, whereas in 5 this is indeed possible without difficulty using even higher content.
Finally, it was found that the inventive examples have better toughness properties than the comparative examples.
Ref.1 -Ref.2 GY 250 (A) 5 Ref.3 MY 790 (A) 5 Ref.4 CY 179 (-) Ref.5 Tixogel0 VZ(C1) 2 100 Ref.6 Tixogel0 VZ (C1) 4 100 CY 179 (-) Ref.7 1 SBM (C3) GY 250 (A) 1 SBM (C3) 4 1 20 GY 250 (A) 2 3.75 1.25 25 RLR1 (C2) GY 250 (A) 3 2.5 2.5 50 RLR1 (C2) GY 250 (A) 4 3.5 1.5 30 Cloisite0 93A (Cl) GY 250 (A) Cloisite0 30 B(C1) 0.8 4.2 84 RLR2 (C2) GY 250 (A) 6 Cloisite0 93A (Cl) 2 3 60 RLR3 (C2) GY 250 (A) 7 Cloisite0 93A (Cl) 3 2 40 RLR3 (C2) Table 1: Composition of examples.
* based on the weight of the composition Test methods Flexural strength, flexural strain, and flexural modulus were measured to DIN EN ISO 178 (determination of flexural properties) on a 1185-5500R Instron tester at 2 mm/min at 23 C, 50% rel. humidity.
Flexural Flexural strain Flexural modulus strength [MPa] [o] [MPa]
Ref.1 51.0 1.6 3175 Ref.2 62.7 2.6 2704 Ref.3 55.8 2.0 2772 Ref.4 14.0 0.5 2614 Ref.5 25.87 0.8 2795 Ref.6 n.m.** n.m.** n.m.**
Ref.7 n.m.** n.m.** n.m.**
1 73.5 3.3 2684 2 77.41 4.65 2267 3 64.58 3.55 2024 4 85.82 4.5 2519 5 86.9 4.1 2709 6 81.73 4.38 2458 7 79.86 3.79 2395 Table 2: Mechanical properties of examples.
n.m. = not measurable Table 2 shows that formulations with technical-grade liquid epoxy resin (Araldite GY 250) which has a proportion of hydroxy-functional oligomers (s > 0 in formula (I)) exhibit better mechanical properties than those exhibited when using bisphenol A diglycidyl ether having no hydroxy groups (Araldite MY 790) (Ref. 2 and Ref. 3). Table 2 moreover shows that when compounds having two glycidyl ether groups, Araldite GY 250 and Araldite MY 790, are compared with Araldite CY 179 (3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane-carboxylate Ref. 4), there is a pronounced improvement in mechanical properties.
The results from the inventive compositions moreover show greatly increased values for mechanical properties. It is also noticeable that the inventive compositions simultaneously exhibit higher values for flexural strength and for flexural strain when compared with the comparative examples.
In the inventive compositions it is possible to achieve higher contents of toughness improvers than in the comparative examples. For example, mixing to achieve homogeneous incorporation using toughness improver content of 4% by weight in compositions is impossible to achieve Ref. 6, whereas in 5 this is indeed possible without difficulty using even higher content.
Finally, it was found that the inventive examples have better toughness properties than the comparative examples.
Claims (31)
1. A composition encompassing at least one compound A which has at least two glycidyl ether groups;
and also encompassing a linear or branched polyester B which is prepared from a macrocyclic poly(.alpha.,.omega.-alkylene terephthalate) or from a macrocyclic poly(.alpha.,.omega.-alkylene 2,6-naphthalenedicarboxylate) in the presence of an organotin catalyst or of an organotitanium catalyst;
and also encompassing at least one toughness improver C.
and also encompassing a linear or branched polyester B which is prepared from a macrocyclic poly(.alpha.,.omega.-alkylene terephthalate) or from a macrocyclic poly(.alpha.,.omega.-alkylene 2,6-naphthalenedicarboxylate) in the presence of an organotin catalyst or of an organotitanium catalyst;
and also encompassing at least one toughness improver C.
2. The composition as claimed in claim 1, characterized in that the compound A which has at least two glycidyl ether groups is a diglycidyl ether of a bisphenol A or of a bisphenol F, or of a bisphenol A/bisphenol F mixture, or is a liquid oligomer thereof.
3. The composition as claimed in claim 1 or 2, characterized in that the linear or branched polyester B is a linear polyester B.
4. The composition as claimed in claim 3, characterized in that the polyester B has the structural formula (II) IMG>
where n = 1, 2, 3, or 4, in particular n = 1 or 3, preferably n = 3;
and where m from 50 to 2000, in particular from 50 to 800, preferably from 50 to 600, particularly preferably from 100 to 600.
where n = 1, 2, 3, or 4, in particular n = 1 or 3, preferably n = 3;
and where m from 50 to 2000, in particular from 50 to 800, preferably from 50 to 600, particularly preferably from 100 to 600.
5. The composition as claimed in claim 3, characterized in that the polyester B has the structural formula (III) where n' = 1, 2, 3, or 4, in particular n' = 1 or 3, preferably n' = 3;
and where m' = from 50 to 200, in particular from 50 to 800, preferably from 50 to 600, particularly preferably from 100 to 600.
and where m' = from 50 to 200, in particular from 50 to 800, preferably from 50 to 600, particularly preferably from 100 to 600.
6. The composition as claimed in any of claims 1 to 5, characterized in that the macrocyclic poly(.alpha.,.omega.-alkylene terephthalate) or the macrocyclic poly(.alpha.,.omega.-alkylene 2,6-naphthalenedicarboxylate) has the structure of the formula (IV) IMG>
where R = ethylene, propylene, butylene, pentylene, in particular ethylene or butylene, preferably butylene;
and IMG>
where the broken lines indicate the bonds to R;
and where p has been selected so that the molar mass Mn of the macrocyclic poly(.alpha.,.omega.-alkylene terephthalate) or of the macrocyclic poly(.alpha.,.omega.-alkylene 2,6-naphthalenedicarboxylate) is from 300 to 2000 g/mol, in particular from 350 to 800 g/mol.
where R = ethylene, propylene, butylene, pentylene, in particular ethylene or butylene, preferably butylene;
and IMG>
where the broken lines indicate the bonds to R;
and where p has been selected so that the molar mass Mn of the macrocyclic poly(.alpha.,.omega.-alkylene terephthalate) or of the macrocyclic poly(.alpha.,.omega.-alkylene 2,6-naphthalenedicarboxylate) is from 300 to 2000 g/mol, in particular from 350 to 800 g/mol.
7. The composition as claimed in any of the preceding claims, characterized in that the toughness improver C
is an ion-exchanged lamellar mineral C1;
or a reactive liquid rubber C2;
or a block copolymer C3 which is obtained from free-radical polymerization of methacrylic ester with at least one further monomer having an olefinic double bond.
is an ion-exchanged lamellar mineral C1;
or a reactive liquid rubber C2;
or a block copolymer C3 which is obtained from free-radical polymerization of methacrylic ester with at least one further monomer having an olefinic double bond.
8. The composition as claimed in claim 7, characterized in that the toughness improver C is an ion-exchanged lamellar mineral C1.
9. The composition as claimed in claim 7, characterized in that the toughness improver C
present in the composition also comprises either a reactive liquid rubber C2 or a block copolymer C3 alongside an ion-exchanged lamellar mineral C1.
present in the composition also comprises either a reactive liquid rubber C2 or a block copolymer C3 alongside an ion-exchanged lamellar mineral C1.
10. The composition as claimed in any of claims 7 to 9, characterized in that the ion-exchanged lamellar mineral C1 is a cation-exchanged lamellar mineral C1c which is obtained from a lamellar mineral C1' in which at least a portion of the cations has been exchanged for organic cations.
11. The composition as claimed in any of claims 7 to 10, characterized in that the lamellar mineral C1' is a phyllosilicate.
12. The composition as claimed in claim 11, characterized in that the lamellar mineral C1' is a kaolinite, a montmorillonite, a hectorite, or an illite.
13. The composition as claimed in any of claims 7 to 9, characterized in that the ion-exchanged lamellar mineral C1 is an anion-exchanged lamellar mineral C1a which is obtained from a lamellar mineral C1" in which at least a portion of the anions has been exchanged for organic anions.
14. The composition as claimed in claim 13, characterized in that the lamellar mineral C1" is a hydrotalcite.
15. The composition as claimed in any of claims 7 to 14, characterized in that the organic cations have the formulae (V), (VI), (VII), (VIII), or (IX) IMG>
where X = N, O, P, or S;
Rl, R1' , R1" , and R1'", independently of each other =
H, C1-C20-alkyl, substituted or unsubstituted aryl;
R2 = H, C1-C2O-alkyl, substituted or unsubstituted aryl;
R3 = H, C1-C2O-alkyl, substituted or unsubstituted aryl, or N (R2) 2;
R4 = H, C1-C20-alkyl, substituted or unsubstituted aryl, or N (R2) 2 R5 = substituent which, together with the N+ shown in formula (V), forms an unsubstituted or substituted ring of from 4 to 9 atoms, and which, if appropriate, has double bonds;
R6 = substituent which, together with the N+ shown in formula (VIII), forms an unsubstituted or substituted bicyclic ring of from 6 to 12 atoms, and which, if appropriate, comprises further heteroatoms or comprises cations of heteroatoms;
R7 = substituent which, together with the N+ shown in formula (IX), forms an unsubstituted or substituted heteroaromatic ring whose size is from to 7 atoms.
where X = N, O, P, or S;
Rl, R1' , R1" , and R1'", independently of each other =
H, C1-C20-alkyl, substituted or unsubstituted aryl;
R2 = H, C1-C2O-alkyl, substituted or unsubstituted aryl;
R3 = H, C1-C2O-alkyl, substituted or unsubstituted aryl, or N (R2) 2;
R4 = H, C1-C20-alkyl, substituted or unsubstituted aryl, or N (R2) 2 R5 = substituent which, together with the N+ shown in formula (V), forms an unsubstituted or substituted ring of from 4 to 9 atoms, and which, if appropriate, has double bonds;
R6 = substituent which, together with the N+ shown in formula (VIII), forms an unsubstituted or substituted bicyclic ring of from 6 to 12 atoms, and which, if appropriate, comprises further heteroatoms or comprises cations of heteroatoms;
R7 = substituent which, together with the N+ shown in formula (IX), forms an unsubstituted or substituted heteroaromatic ring whose size is from to 7 atoms.
16. The composition as claimed in any of claims 7 to 15, characterized in that the reactive liquid rubber C2 is a polyurethane prepolymer terminated by glycidyl ether groups.
17. The composition as claimed in claim 16, characterized in that the reactive liquid rubber C2 has the formula (X) IMG>
where Y1 is a q-valent radical of a polyurethane linear or branched prepolymer terminated by isocyanate groups, after removal of the terminal isocyanate groups;
Y2 is a radical of an aliphatic, cycloaliphatic, aromatic, or araliphatic epoxide comprising a primary or secondary hydroxy group, after removal of the hydroxide groups and epoxide groups;
q = 2, 3, or 4; and r = 1, 2, or 3.
where Y1 is a q-valent radical of a polyurethane linear or branched prepolymer terminated by isocyanate groups, after removal of the terminal isocyanate groups;
Y2 is a radical of an aliphatic, cycloaliphatic, aromatic, or araliphatic epoxide comprising a primary or secondary hydroxy group, after removal of the hydroxide groups and epoxide groups;
q = 2, 3, or 4; and r = 1, 2, or 3.
18. The composition as claimed in any of claims 7 to 17, characterized in that the at least one further monomer which is used for preparation of the block copolymer C3 and which has an olefinic double bond is selected from the group consisting of styrene, butadiene, acrylonitrile, and vinyl acetate.
19. The composition as claimed in claim 18, characterized in that the block copolymer C3 is a block copolymer composed of methyl methacrylate, styrene, and butadiene.
20. The composition as claimed in any of the preceding claims, characterized in that the amount of toughness improver C is from 10 to 85% by weight, based on the total weight of A + C.
21. The composition as claimed in any of the preceding claims, characterized in that the amount of linear or branched polyester B is from 85 to 98% by weight of the composition.
22. A process for preparation of a composition as claimed in any of claims 1 to 21, characterized in that it encompasses the following steps:
- formation of a premix AC of toughness improver C and of the compound A which has at least two glycidyl ether groups, - addition of the mixed premix AC to the macrocyclic poly(.alpha.,.omega.-alkylene terephthalate) or macrocyclic poly(.alpha.,.omega.-alkylene 2,6-naphthalenedicarboxylate) which has been mixed with the organotin catalyst or organotitanium catalyst.
- formation of a premix AC of toughness improver C and of the compound A which has at least two glycidyl ether groups, - addition of the mixed premix AC to the macrocyclic poly(.alpha.,.omega.-alkylene terephthalate) or macrocyclic poly(.alpha.,.omega.-alkylene 2,6-naphthalenedicarboxylate) which has been mixed with the organotin catalyst or organotitanium catalyst.
23. The process as claimed in claim 22, characterized in that preparation of the linear or branched polyester B takes place at a temperature of from 160°C to 220°C, in particular from 160°C to 200°C, in the presence of the premix AC.
24. The use of a premix AC of toughness improver C and of the compound A which has at least two glycidyl ether groups in preparation of the linear or branched polyester B as described in claims 1 to 21.
25. A composite product encompassing a composition as claimed in any of claims 1 to 21 and also comprising fibers, where the fibers have been selected from the group consisting of glass fibers, metal fibers, carbon fibers, aramid fibers, mineral fibers, plant fibers, and mixtures thereof.
26. The composite product as claimed in claim 25, characterized in that the fibers are carbon fibers or metal fibers, in particular steel fibers.
27. The composite product as claimed in claim 25 or 26, characterized in that the proportion of fibers is from 30 to 65% by volume, based on the volume of the composite product.
28. The composite product as claimed in any of claims 25 to 27, characterized in that the shape of the composite product is sheet-like.
29. A process for production of a composite product as claimed in any of claims 25 to 28, characterized in that the molten composition is brought into contact with the fibers and is solidified via cooling in a mold.
30. The process as claimed in claim 29, characterized in that the mold has an outlet through which the composite product is continuously discharged during cooling.
31. The use of a composite product as claimed in any of claims 25 to 28, or of a composite product produced by a process as claimed in claim 29 or 30, for the structural reinforcement of construction work or of a conveyance.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP05100126A EP1679341A1 (en) | 2005-01-11 | 2005-01-11 | Impact resistant composition |
| EP05100126.1 | 2005-01-11 | ||
| PCT/EP2006/050158 WO2006075009A1 (en) | 2005-01-11 | 2006-01-11 | Impact-resistant compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2593606A1 true CA2593606A1 (en) | 2006-07-20 |
| CA2593606C CA2593606C (en) | 2014-09-23 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2593606A Expired - Fee Related CA2593606C (en) | 2005-01-11 | 2006-01-11 | Impact-resistant compositions |
Country Status (6)
| Country | Link |
|---|---|
| EP (2) | EP1679341A1 (en) |
| JP (1) | JP2008527099A (en) |
| KR (1) | KR20070110850A (en) |
| CN (1) | CN101128524B (en) |
| CA (1) | CA2593606C (en) |
| WO (1) | WO2006075009A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1932648A1 (en) | 2006-12-15 | 2008-06-18 | Sika Technology AG | Structural reinforcement material, insert, and reinforced cavity comprising same |
| JP5756025B2 (en) * | 2009-12-14 | 2015-07-29 | アロン化成株式会社 | Thermoplastic elastomer composition and method for producing the same |
| US20200399433A1 (en) * | 2016-11-30 | 2020-12-24 | Sabic Global Technologies B.V. | Improvement of impact properties of dynamically cross-linked networks by using reactive impact modifiers |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE541648A (en) * | 1955-04-07 | 1900-01-01 | ||
| US5530052A (en) * | 1995-04-03 | 1996-06-25 | General Electric Company | Layered minerals and compositions comprising the same |
| US5498651A (en) * | 1995-06-19 | 1996-03-12 | General Electric Company | Method for polymerizing macrocyclic polyester oligomers |
| EP1060211B1 (en) * | 1998-02-20 | 2003-04-23 | Vantico AG | Organophilic phyllosilicates |
| EP1431325A1 (en) * | 2002-12-17 | 2004-06-23 | Sika Technology AG | Heat-curable epoxy resin composition with improved low-temperatur impact strength |
| AU2003300010A1 (en) * | 2002-12-20 | 2004-07-22 | Dow Global Technologies Inc. | Polymerized macrocyclic oligomer nanocomposite compositions |
| EP1578591A1 (en) * | 2002-12-23 | 2005-09-28 | Dow Global Technologies Inc. | Method of smc molding |
-
2005
- 2005-01-11 EP EP05100126A patent/EP1679341A1/en not_active Withdrawn
-
2006
- 2006-01-11 CN CN2006800060449A patent/CN101128524B/en not_active Expired - Fee Related
- 2006-01-11 KR KR1020077018574A patent/KR20070110850A/en not_active Application Discontinuation
- 2006-01-11 CA CA2593606A patent/CA2593606C/en not_active Expired - Fee Related
- 2006-01-11 WO PCT/EP2006/050158 patent/WO2006075009A1/en active Application Filing
- 2006-01-11 JP JP2007549912A patent/JP2008527099A/en active Pending
- 2006-01-11 EP EP06700275A patent/EP1844094A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
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| JP2008527099A (en) | 2008-07-24 |
| EP1679341A1 (en) | 2006-07-12 |
| CA2593606C (en) | 2014-09-23 |
| KR20070110850A (en) | 2007-11-20 |
| EP1844094A1 (en) | 2007-10-17 |
| CN101128524A (en) | 2008-02-20 |
| WO2006075009A1 (en) | 2006-07-20 |
| CN101128524B (en) | 2011-02-02 |
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