Semi-aromatic polyamide resin, composite material, preparation method and application thereof

Abstract

The present application relates to a semi-aromatic polyamide resin, a composite material, a preparation method and an application. The raw materials for preparing the semi-aromatic polyamide resin include diamine, dicarboxylic acid and mercapto monocarboxylic acid; the dicarboxylic acid includes substituted or unsubstituted C 6~20 Aromatic dibasic acid. The semi-aromatic polyamide resin is made of diamine, dicarboxylic acid and mercapto monocarboxylic acid as raw materials; the mercapto monocarboxylic acid contains mercapto groups, and the introduction of mercapto monocarboxylic acid into the polymer can form a thioester group. The sulfur atom in the thioester group forms a coordination bond with the transition metal particles in the metal bracket of the LED lamp, so that the semi-aromatic polyamide resin can be tightly bonded to the metal bracket, thereby improving the adhesion performance of the LED semi-aromatic polyamide resin to the metal bracket.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, in particular to a semi-aromatic polyamide resin, a composite material, and a preparation method and application thereof. Background Art

[0002] LED light sources are mainly composed of semiconductor chips, LED light source reflective metal brackets, gold wires, and packaging plastics. The LED packaging process goes through steps such as solid crystal, wire bonding, and packaging plastic curing to fix the semiconductor chip and gold wires on the metal bracket, and encapsulate them in the space surrounded by the metal bracket and the packaging plastic. The LED light source reflective metal bracket is the "skeleton" of the LED light source and also a functional part. The LED reflective bracket reflects the light emitted by the LED chip at a certain angle to reduce light loss, and then passes through the packaging plastic material to form a light source for LED lighting or display.

[0003] During the curing process of the encapsulated plastic, the LED reflector bracket needs to be exposed to a temperature of 150℃~200℃ for 6 hours to 10 hours. At the same time, when the encapsulated lamp beads are made into display screens, they need to pass the pins through the holes on the circuit board and then be welded, just like SMT (a technology that directly welds electronic components on the surface of a printed circuit board (PCB)). This requires that the LED metal bracket and the encapsulated plastic will not deform during the encapsulation and SMT, and will not be damaged under load; thus, higher requirements are placed on the tightness between the LED metal bracket material and the encapsulated plastic.

[0004] Traditional polyamide resin has poor adhesion to the metal material in the bracket, which reduces the quality of the LED lamp. Summary of the invention

[0005] Based on this, it is necessary to provide a semi-aromatic polyamide resin having good adhesion to a metal bracket and a preparation method thereof. Furthermore, a semi-aromatic polyamide composite material and a preparation method and application thereof are provided.

[0006] The first aspect of the present application provides a semi-aromatic polyamide resin, wherein the raw materials for preparing the semi-aromatic polyamide resin include diamine, dicarboxylic acid and mercapto monocarboxylic acid; the dicarboxylic acid includes substituted or unsubstituted C 6~20 Aromatic dibasic acid.

[0007] The semi-aromatic polyamide resin is made of diamine, dicarboxylic acid and mercapto monocarboxylic acid as raw materials; the mercapto monocarboxylic acid contains mercapto groups, and the mercapto monocarboxylic acid is introduced into the polymer to form a thioester group. The sulfur atom in the thioester group forms a coordination bond with the transition metal particles in the metal bracket of the LED lamp, so that the semi-aromatic polyamide resin can be tightly bonded to the metal bracket, thereby improving the adhesion performance of the LED semi-aromatic polyamide resin with the metal bracket.

[0008] At the same time, the mercapto group (-SH) in the mercapto monocarboxylic acid is less acidic than the carboxyl group (-COOH). The mercapto group can replace part of the carboxyl group for end-capping, thereby reducing the end group reaction activity of the polyamide, making the polyamide nylon resin in a sub-active state, and then making the molecular chains of the semi-aromatic polyamide resin cross-linked again during secondary recycling, thereby effectively inhibiting the significant decrease in the mechanical properties of the semi-aromatic polyamide resin during repeated use.

[0009] In some embodiments, the diamine comprises a substituted or unsubstituted C 6~12 diamine; and / or

[0010] The number of carbon atoms in the mercaptomonocarboxylic acid is 2 to 12; and / or

[0011] The C 8~20 The aromatic dicarboxylic acid comprises at least one of phthalic acid, naphthalene dicarboxylic acid and biphenyl dicarboxylic acid; and / or

[0012] The dicarboxylic acid also includes substituted or unsubstituted C 2~12 Aliphatic dicarboxylic acids.

[0013] In some embodiments, the diamine includes 1,6-hexanediamine, or the diamine includes substituted or unsubstituted C 6~12 Branched diamines, substituted or unsubstituted C 7~12 At least one of the linear diamines and 1,6-hexanediamine; optionally, the diamines include at least one of 1,9-nonanediamine, 1,10-decanediamine, lauryl diamine, 1-4-butanediamine and 1,4-diaminocyclohexane and 1,6-hexanediamine.

[0014] In some embodiments, the mercaptomonocarboxylic acid is selected from at least one of mercaptoacetic acid and mercaptopropionic acid; and / or,

[0015] The dicarboxylic acid includes at least one of isophthalic acid, 1,4-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,2-biphenyl dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 1,10 sebacic acid, 1,12-dodecane dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid and diphenyl sulfone-4,4'-dicarboxylic acid, and terephthalic acid.

[0016] In some embodiments, each of the substituted groups is independently selected from one of C1~C9 alkyl, amino, halogen, nitro, hydroxyl, thiol, carboxyl and cyano.

[0017] In some embodiments, the molar ratio of the diamine, the dicarboxylic acid and the mercapto monocarboxylic acid is 1:1:(0.03-0.1).

[0018] The second aspect of the present application provides a semi-aromatic polyamide resin, comprising a segment structure represented by formula (I):

[0019]

[0020] Formula (I);

[0021] wherein R1 and R4 are each independently selected from substituted or unsubstituted C 6~18 Arylene or substituted or unsubstituted C 1~10 One of the alkylene groups, at least one of R1 and R4 is a substituted or unsubstituted C 6~18 Arylene; R2 is substituted or unsubstituted C1~ 12 Alkylene; R3 is substituted or unsubstituted C 1~11 of alkylene.

[0022] In some embodiments, the semi-aromatic polyamide resin satisfies at least one of the following conditions:

[0023] (1) R1 is p-phenyl or m-phenyl;

[0024] (2) R2 is C6~C 12 Alkylene;

[0025] (3) R3 is a C1~C3 alkylene group;

[0026] (4) R4 is p-phenyl, m-phenyl or C 1~10 Alkylene.

[0027] The third aspect of the present application provides a method for preparing a semi-aromatic polyamide resin, comprising the following steps:

[0028] The diamine, dicarboxylic acid and mercapto monocarboxylic acid are mixed and prepolymerized to prepare a prepolymer; the dicarboxylic acid includes substituted or unsubstituted C 8~20 Aromatic dicarboxylic acids;

[0029] The prepolymer is subjected to a solid phase viscosity enhancement treatment to prepare the semi-aromatic polyamide resin.

[0030] In some embodiments, the preparation method satisfies at least one of the following conditions:

[0031] (1) The prepolymerization step comprises:

[0032] Under the protection of inert gas, heat up to 160℃~200℃ at a rate of 3℃ / min~10℃ / min, and react at constant temperature for 30min~90min; then heat up to 250℃~300℃ at a rate of 1℃ / min~5℃ / min, and react at constant temperature for 3h~6h under stirring conditions of 70rpm~100rpm;

[0033] (2) The conditions of the solid phase viscosity enhancement treatment include: temperature of 250°C to 280°C, vacuum degree of 20Pa to 60Pa, and time of 1.5h to 2h.

[0034] In some embodiments, the prepolymerization reaction is carried out under the action of a catalyst;

[0035] The catalyst is selected from at least one of sulfuric acid, phosphorous acid, sodium phosphite and p-toluenesulfonic acid; and / or,

[0036] The added amount of the catalyst is 0.1% to 0.5% of the total mass of the diamine, the dicarboxylic acid and the mercapto monocarboxylic acid.

[0037] In a fourth aspect, the present application provides a semi-aromatic polyamide composite material, comprising the following components by weight:

[0038] 40 to 70 parts of the semi-aromatic polyamide resin described in the first or second aspect of the present application or the semi-aromatic polyamide resin prepared by the preparation method described in the third aspect of the present application, 5 to 30 parts of reinforcing filler, 5 to 50 parts of white pigment and 0 to 5 parts of additives.

[0039] In some embodiments, the semi-aromatic polyamide composite material satisfies at least one of the following conditions:

[0040] (1) The reinforcing filler comprises wollastonite fibers; the average diameter of the wollastonite fibers is 1 μm to 25 μm, and the average length is 10 μm to 250 μm;

[0041] (2) The white pigment includes titanium dioxide;

[0042] (3) The additive includes at least one of an antioxidant, a whitening agent and a lubricant; the antioxidant is selected from a phenolic antioxidant or an amine antioxidant; the whitening agent is selected from at least one of magnesium oxide, zinc oxide and calcium oxide; the lubricant is selected from at least one of calcium stearate, zinc stearate, OP wax and PE wax.

[0043] A fifth aspect of the present application provides a method for preparing a semi-aromatic polyamide composite material, comprising the following steps:

[0044] Providing raw materials according to the components of the semi-aromatic polyamide composite material described in the fourth aspect of the present application;

[0045] The raw materials are mixed and extruded to obtain the semi-aromatic polyamide composite material.

[0046] The sixth aspect of the present application provides a use of the semi-aromatic polyamide composite material described in the fourth aspect of the present application in the preparation of polyamide products.

[0047] The seventh aspect of the present application provides a packaging film, comprising the semi-aromatic polyamide composite material described in the fourth aspect of the present application.

[0048] An eighth aspect of the present application provides an LED lamp, comprising a chip, a bracket, and the packaging film provided in the seventh aspect of the present application, wherein the chip is arranged on the bracket, and the packaging film covers the chip.

[0049] A ninth aspect of the present application is an electronic device, comprising the LED lamp described in the eighth aspect of the present application. DETAILED DESCRIPTION

[0050] In order to facilitate the understanding of the present invention, the present application is described in more detail below. Preferred embodiments of the present invention are provided. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. It should be understood that the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0051] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0052] the term

[0053] Unless otherwise specified or incompatible herewith, the terms and phrases used herein shall have the following meanings:

[0054] The term "alkyl" refers to a saturated hydrocarbon containing primary (normal) carbon atoms, or secondary carbon atoms, or tertiary carbon atoms, or quaternary carbon atoms, or a combination thereof. A phrase containing the term, for example, "C1-C9 alkyl" refers to an alkyl containing 1 to 9 carbon atoms, and each occurrence may be independently C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl or C9 alkyl. Suitable examples include, but are not limited to, methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1-propyl (n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (i-Pr, i-propyl, -CH(CH3)2), 1-butyl (n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-1-propyl (i-Bu, i-butyl, -CH2CH(CH3)2), 2-butyl (s-Bu, s-butyl, -CH(C H3)CH2CH3), 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH3)3), 1-pentyl (n-pentyl, -CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2), 3-methyl-1-butyl (- CH2CH2CH(CH3)2), 2-methyl-1-butyl (-CH2CH(CH3)CH2CH3), 1-hexyl (-CH2CH2CH2CH2CH2CH3), 2-hexyl (-CH(CH3)CH2CH2CH2CH3), 3-hexyl (-CH(CH2CH3)(CH2CH2CH3)), 2-methyl-2-pentyl (-C(CH3)2CH2CH2CH3), 3-methyl-2-pentyl (-CH(CH3)CH( 2), 2-methyl-3-pentyl (-CH(CH2CH3)CH(CH3)2), 2,3-dimethyl-2-butyl (-C(CH3)2CH(CH3)2), 3,3-dimethyl-2-butyl (-CH(CH3)C(CH3)3 and octyl (-(CH2)7CH3).

[0055] "Alkylene" refers to a hydrocarbon group with two monovalent radical centers derived from an alkyl group by removing a hydrogen atom, which can be a saturated branched alkyl group or a saturated straight chain alkyl group. 12"Alkylene" means that the alkyl portion contains 1 to 12 carbon atoms and each occurrence can be independently C1 alkylene, C4 alkylene, C5 alkylene, C6 alkylene, C7 alkylene, C8 alkylene or C9 alkylene. Suitable examples include, but are not limited to, methylene (-CH2-), 1,1-ethyl (-CH(CH3)-), 1,2-ethyl (-CH2CH2-), 1,1-propyl (-CHCH2(CH3)-), 1,2-propyl (-CH2CH(CH3)-), 1,3-propyl (-CH2CH2CH2-) and 1,4-butyl (-CH2CH2CH2CH2-).

[0056] "Aryl" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing a hydrogen atom, which can be a monocyclic aromatic group, a condensed aromatic group, or a polycyclic aromatic group. For polycyclic rings, at least one is an aromatic ring system. For example, "C6-C20 aromatic group" refers to an aromatic group containing 5 to 20 carbon atoms, and each time it appears, it can be independently C6 aromatic group, C10 aromatic group, C14 aromatic group, C18 aromatic group or C20 aromatic group. Suitable examples include, but are not limited to, benzene, biphenyl, naphthalene, anthracene, phenanthrene, diphenylene, triphenylene and its derivatives. It is understandable that multiple aromatic groups can also be interrupted by short non-aromatic units (e.g., <10% non-H atoms, such as C, N or O atoms), such as acenaphthene, fluorene, or 9,9-diarylfluorene, triarylamine, diaryl ether system should also be included in the definition of aromatic group.

[0057] "Arylene" refers to a divalent group formed by removing two hydrogen atoms from aromatic hydrocarbons (such as benzene, naphthalene, etc.). It is an organic group containing an aromatic structure. Taking the benzene-derived arylene as an example, it is usually represented by -(C6H4)-, which connects two other groups and maintains the partial aromaticity and conjugated structure of the benzene ring. Compared with aryl groups, arylene groups have two connection sites and can play a bridging role in the construction of organic compounds.

[0058] "Halogen" or "halo" refers to F, Cl, Br or I.

[0059] In one embodiment of the present application, a semi-aromatic polyamide resin is provided. The raw materials for preparing the semi-aromatic polyamide resin include diamine, dicarboxylic acid and mercapto monocarboxylic acid; the dicarboxylic acid includes substituted or unsubstituted C 8~20 Aromatic dibasic acid.

[0060] The semi-aromatic polyamide resin is made of diamine, dicarboxylic acid and mercapto monocarboxylic acid as raw materials; the mercapto monocarboxylic acid contains mercapto groups, and the mercapto monocarboxylic acid is introduced into the polymer to form a thioester group. The sulfur atom in the thioester group forms a coordination bond with the transition metal particles in the metal bracket of the LED lamp, so that the semi-aromatic polyamide resin can be tightly bonded to the metal bracket, thereby improving the adhesion performance of the LED semi-aromatic polyamide resin with the metal bracket.

[0061] At the same time, the mercapto group (-SH) in the mercapto monocarboxylic acid is less acidic than the carboxyl group (-COOH). The mercapto group can replace part of the carboxyl group for end-capping, thereby reducing the end group reaction activity of the polyamide, making the polyamide nylon resin in a sub-active state, and then making the molecular chains of the semi-aromatic polyamide resin cross-linked again during secondary recycling, thereby effectively inhibiting the significant decrease in the mechanical properties of the semi-aromatic polyamide resin during repeated use.

[0062] C8~20 aromatic dicarboxylic acids refer to a type of carboxylic acid with a carbon number between 8 and 20, containing a benzene ring and two carboxyl groups.

[0063] In some embodiments, the dicarboxylic acid comprises a combination of one or more of phthalic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid and 5-methylisophthalic acid. Preferably, the dicarboxylic acid comprises at least phthalic acid. Further, the dicarboxylic acid comprises at least terephthalic acid.

[0064] In some embodiments, the dicarboxylic acid further includes substituted or unsubstituted C2~12 aliphatic dicarboxylic acids. The C2~12 aliphatic dicarboxylic acids may be straight-chain dicarboxylic acids having 2 to 12 carbon atoms, such as oxalic acid, 1,4-succinic acid, 1,6-hexanodioic acid, 1,8-octanedioic acid, 1,9-nonanediol, 1,10-semendiol and 1,12-dodecanedioic acid. It may also be a dicarboxylic acid having 4 to 12 carbon atoms and containing a branched chain, such as 2-methylsuccinic acid, 2-ethylhexanodioic acid and 3,5,5-trimethylhexanodioic acid.

[0065] In some embodiments, the dicarboxylic acid includes terephthalic acid and at least one of isophthalic acid, 1,4-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,2-biphenyl dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 1,10 sebacic acid, 1,12-dodecane dicarboxylic acid, 1,9-zelaic acid, and 1,8-octanedioic acid.

[0066] In some embodiments, the number of carbon atoms in the mercaptomonocarboxylic acid is 2 to 12. As an example, the number of carbon atoms in the mercaptomonocarboxylic acid can be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.

[0067] In some embodiments, the mercaptomonocarboxylic acid is selected from at least one of thioglycolic acid and mercaptopropionic acid.

[0068] In some embodiments, the diamine includes 1,6-hexanediamine.

[0069] In some embodiments, the diamine further comprises at least one of substituted or unsubstituted C6~12 branched diamines and substituted or unsubstituted C7~12 straight-chain diamines. The C6~12 branched diamine refers to a diamine having a branched structure with 6 to 12 carbon atoms, wherein the branch can be an alkyl, aromatic, heteroaromatic or aralkyl group. As an example, the C6~12 branched diamine can be 3-methyl-1,7-heptanediamine, 2-methyl-1,6-hexanediamine, 4,4'-dimethyl-1,10-decanediamine and 4-methyl-1,8-octanediamine. 7~12 Straight-chain diamines are diamines in which all carbon atoms are in one molecular chain. For example, unsubstituted C 7~12 The linear diamine may be 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, or 1,12-dodecanediamine.

[0070] In some embodiments, the diamine includes at least one of 1,9-nonanediamine, 1,10-decanediamine, lauryldiamine, 1-4-butanediamine, and 1,4-diaminocyclohexane and 1,6-hexanediamine.

[0071] In some embodiments, each of the above-mentioned substituted groups is independently selected from one of C1~C9 alkyl, amino, halogen, nitro, hydroxyl, thiol, carboxyl and cyano.

[0072] In some embodiments, the molar ratio of the diamine, the dicarboxylic acid and the mercapto monocarboxylic acid is 1:1:(0.03-0.1), and can be 1:1:0.03, 1:1:0.05, 1:1:0.08 or 1:1:0.1.

[0073] In some embodiments, the semi-aromatic polyamide resin has a number average molecular weight of 6,000 to 20,000.

[0074] In some embodiments, the whiteness of the semi-aromatic polyamide resin is 75-85.

[0075] In one embodiment of the present application, a semi-aromatic polyamide resin is provided, comprising a segment of a structure of formula (I):

[0076]

[0077] Formula (I);

[0078] wherein R1 and R4 are each independently selected from substituted or unsubstituted C 6~20 Arylene or substituted or unsubstituted C 1~10 One of the alkylene groups, at least one of R1 and R4 is a substituted or unsubstituted C 6~20 Arylene; R2 is substituted or unsubstituted C1~ 12 Alkylene; R3 is substituted or unsubstituted C 1~11 of alkylene.

[0079] In some embodiments, R1 is p-phenyl or m-phenyl. Preferably, R1 is p-phenyl.

[0080] In some embodiments, R2 is C6~C 12 Preferably, R2 is 1,6-hexyl (-CH2CH2CH2CH2CH2CH2-).

[0081] In some embodiments, R3 is a C1-C3 alkylene group. Preferably, R3 is a methylene group (-CH2-) or a 1,3-propyl group (-CH2CH2CH2-).

[0082] In some embodiments, R4 is p-phenyl, m-phenyl or C 1~10 Preferably, R4 is m-phenyl, 1,8-octyl (-CH2CH2CH2CH2CH2CH2CH2CH2-) or 1,10-decyl (-CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-).

[0083] In some embodiments, the semi-aromatic polyamide resin comprises a segment of the structure of formula (II):

[0084]

[0085] Formula (II),

[0086] Wherein, R5 is selected from substituted or unsubstituted C6~ 12 As an example, R5 can be 1,6-hexyl (-CH2CH2CH2CH2-), 1,9-nonyl (-CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-), 1,10-decyl (-CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-), or 1,12-dodecyl (-CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-).

[0087] In another embodiment of the present application, a method for preparing a semi-aromatic polyamide resin is provided, comprising the following steps:

[0088] The diamine, the dicarboxylic acid and the mercapto monocarboxylic acid are mixed and prepolymerized to prepare a prepolymer;

[0089] The prepolymer is subjected to solid phase viscosity enhancement treatment to prepare a semi-aromatic polyamide.

[0090] In some embodiments, the prepolymerization reaction is carried out in the presence of a catalyst.

[0091] In some embodiments, the catalyst is selected from at least one of sulfuric acid, phosphorous acid, sodium phosphite and p-toluenesulfonic acid.

[0092] In some embodiments, the amount of catalyst added is 0.1% to 0.5% of the total mass of the diamine, the dicarboxylic acid and the mercapto monocarboxylic acid.

[0093] In some embodiments, the step of prepolymerization comprises:

[0094] Under the protection of inert gas, heat up to 160℃~200℃ at a rate of 3℃ / min~10℃ / min, and react at constant temperature for 30min~90min; then heat up to 250℃~300℃ at a rate of 1℃ / min~5℃ / min, and react at constant temperature for 3h~6h under stirring conditions of 70rpm~100 rpm.

[0095] In some embodiments, the conditions of the solid phase viscosity enhancement treatment include: a temperature of 250° C. to 280° C., a vacuum degree of 20 Pa to 60 Pa, and a time of 1.5 h to 2 h.

[0096] In one embodiment of the present application, a semi-aromatic polyamide composite material is provided, which includes the following components, measured by mass: 40 to 70 parts of the semi-aromatic polyamide resin as described above or a semi-aromatic polyamide resin prepared by the preparation method as described above, 5 to 30 parts of reinforcing filler, 5 to 50 parts of white pigment, and 0 to 5 parts of additives.

[0097] The semi-aromatic polyamide composite material further comprises reinforcing fillers and white pigments of specific components on the basis of the semi-aromatic polyamide resin of specific structure; using it as the packaging plastic for LED lamps can improve the closeness between the packaging plastic and the metal bracket, thereby effectively suppressing the loss of light emitted by the chip and improving the luminous effect of the LED lamp. Furthermore, the semi-aromatic polyamide composite material can further improve the whiteness of the semi-aromatic polyamide composite material and is not easy to yellow through the synergistic effect of each component.

[0098] As an example, in the semi-aromatic polyamide composite material, the mass fraction of the semi-aromatic polyamide resin can be 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts or 70 parts. Further, the mass fraction of the semi-aromatic polyamide resin can be a range value consisting of any two of the above point values ​​as end values.

[0099] As an example, in the semi-aromatic polyamide composite material, the mass fraction of the reinforcing filler can be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts or 30 parts. Further, the mass fraction of the reinforcing filler can be a range value consisting of any two of the above point values ​​as end values.

[0100] As an example, in the semi-aromatic polyamide composite material, the mass fraction of white pigment can be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts or 50 parts. Further, the mass fraction of white pigment can be a range value consisting of any two of the above point values ​​as end values.

[0101] As an example, in the semi-aromatic polyamide composite material, the mass fraction of the additive can be 0, 1, 2, 3, 4 or 5. Further, the mass fraction of the additive can be a range value consisting of any two of the above point values ​​as end values.

[0102] In some embodiments, the reinforcing filler is an inorganic reinforcing filler; further, it can be at least one of wollastonite, wollastonite fiber and glass fiber.

[0103] In some embodiments, the wollastonite fibers have an average diameter of 1 μm to 25 μm and an average length of 10 μm to 250 μm. Preferably, the wollastonite fibers have an average diameter of 4 μm to 20 μm and an average length of 45 μm to 200 μm.

[0104] In some embodiments, the white pigment includes titanium dioxide.

[0105] In some embodiments, the additives include at least one of an oxidizing agent, a whitening agent, and a lubricant.

[0106] In some embodiments, the oxidant is selected from at least one of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine N445 antioxidant and antioxidant 412s. Preferably, the oxidant is antioxidant 412s. Oxidant 412s contains -S- groups, which can make the material less likely to turn yellow and extend the anti-yellowing time of the material.

[0107] In some embodiments, the whitening agent is selected from at least one of calcium oxide, magnesium oxide and zinc oxide. Adding the whitening agent can improve the whiteness and glossiness of the composition product.

[0108] In some embodiments, the lubricant is selected from at least one of calcium stearate, OP wax, E wax and PE wax.

[0109] In one embodiment of the present application, a semi-aromatic polyamide composite material is provided which is prepared by using the above-mentioned semi-aromatic polyamide composite material.

[0110] In one embodiment of the present application, a method for preparing a semi-aromatic polyamide composite material is provided, comprising the following steps:

[0111] The semi-aromatic polyamide composite material is mixed and extruded to obtain a semi-aromatic polyamide composite material.

[0112] In some embodiments, a screw extruder is used for mixing and extrusion, and the temperature setting range of the screw extruder is 280° C. to 330° C.

[0113] In some embodiments, the rotation speed of the screw extruder is 400 r / min to 500 r / min.

[0114] In one embodiment of the present application, there is provided application of the above-mentioned semi-aromatic polyamide composite material in the preparation of polyamide products.

[0115] In some embodiments, the polyamide product includes but is not limited to an encapsulation film for LED lamps.

[0116] In one embodiment of the present application, a packaging film is provided. The packaging film includes the above-mentioned semi-aromatic polyamide composite material.

[0117] In one embodiment of the present application, an LED lamp is provided, comprising a chip, a bracket and the above-mentioned packaging film, wherein the chip is arranged on the bracket and the packaging film covers the chip.

[0118] An embodiment of the present application provides an electronic device, wherein the electronic device includes an LED lamp.

[0119] In order to make the purpose, technical solutions and advantages of the present invention more concise and clear, the present invention is described with the following specific embodiments, but the present invention is by no means limited to these embodiments. The embodiments described below are only preferred embodiments of the present invention, which can be used to describe the present invention and cannot be understood as limiting the scope of the present invention. It should be pointed out that any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

[0120] In order to better illustrate the present invention, the present invention is further described below in conjunction with the embodiments. The following are specific embodiments.

[0121] Example 1

[0122] Preparation of semi-aromatic polyamide resin:

[0123] (1) Prepolymerization: Put polymerization monomers (hexamethylenediamine, 2-methyl-1,5-pentanediamine, terephthalic acid, isophthalic acid, thioglycolic acid, 3-mercaptopropionic acid, etc.), end-capping agent benzoic acid, catalyst (sulfuric acid, the amount is 0.2% of the total amount of all monomers) and deionized water into a stainless steel high-pressure reactor equipped with mechanical stirring. After evacuating and replacing with N2 three times, start heating and stirring, and heat to 180℃ at a rate of 5℃ / min. After keeping the temperature constant for 60min, heat to 270℃ at a rate of 2℃ / min, stir slowly and keep the temperature constant for 4h to allow the prepolymerization reaction to proceed fully. After the constant temperature ends, slowly raise the temperature to 280℃ and start draining to normal pressure. When the pressure drops to normal pressure, close the drain valve, the reaction is over, and the temperature drops to room temperature for discharge.

[0124] (2) Solid phase viscosity enhancement: The material prepared in the prepolymerization process is placed in a vacuum drum, the drum speed is set at 10 r / min, and the vacuum degree is set at 40 Pa. The temperature is increased at a rate of 20°C / min. When the temperature reaches 265°C, a sample is taken to test the viscosity, and the discharge end point is determined based on the viscosity result.

[0125] The raw material formula of the semi-aromatic polyamide resin prepared in Example 1 is shown in Table 1.

[0126] Performance Test:

[0127] Whiteness: The polyamide molding composition was injection molded and prepared into a test piece with a length of 60 mm, a width of 60 mm, and a thickness of 1 mm. The color space parameters L, a, and b values ​​were measured using a ColorEye 7000A colorimeter, and then the whiteness W was calculated according to the following formula: H Values:

[0128] W H =100-[(100-L) 2 +a 2 +b 2 ] 1 / 2 .

[0129] Table 1

[0130]

[0131] Note: The number of each raw material component in Table 1 refers to the number of molar weights; the amount of catalyst refers to the ratio of the mass of the catalyst to the total amount of the diamine, dicarboxylic acid and mercapto monocarboxylic acid.

[0132] Embodiments 2 to 21

[0133] The semi-aromatic polyamide resins used in the polyamide composite materials prepared in Examples 2 to 21 are the semi-aromatic polyamide resins prepared in Example 1; other raw material information is as follows:

[0134] Reinforcement material: wollastonite fiber, commercially available; specifically:

[0135] Wollastonite A: average diameter is 13 μm, average length is 80 μm;

[0136] Wollastonite B: average diameter 8 μm, average length 150 μm;

[0137] Wollastonite C: average diameter 4 μm, average length 60 μm;

[0138] Wollastonite D: The average diameter is 20 μm and the average length is 210 μm.

[0139] Pigment: titanium dioxide, commercially available;

[0140] Antioxidant: N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine CAS: 108-26-1 N445, commercially available;

[0141] Brighteners: magnesium oxide, calcium oxide, zinc oxide; commercially available.

[0142] The specific preparation steps are:

[0143] According to the raw material component ratio of each composite material in Table 2, the raw materials were added into a mixer and mixed evenly, and then extruded and granulated by a twin-screw extruder to obtain a PA6T / X composite material; wherein the screw temperature range is 280°C~330°C; and the rotation speed is 450r / min.

[0144] The composition ratios of the compositions prepared in Examples 2 to 21 are shown in Tables 2 and 3.

[0145] Comparative Examples 1 to 4

[0146] The preparation methods of Comparative Examples 1 to 4 are basically the same as those of Examples 2 to 21, except that the raw material component formulas of the composite materials are different. The raw material formulas of Comparative Examples 1 to 4 are shown in Tables 2 and 3.

[0147] Table 2

[0148]

[0149] Table 3

[0150]

[0151] Note: The parts in Table 2 and Table 3 represent the mass parts of each component.

[0152] Performance testing:

[0153] Closeness: The polyamide composite material sample is tested with red ink to characterize the closeness of the bracket plastic and hardware: the LED reflector cup formed by in-mold injection molding of the LED bracket material and the electroplated hardware material strip is immersed in red ink to make the red ink. If the red ink does not penetrate into the reflector cup for 5 minutes, the closeness level is determined to be A; if the red ink does not penetrate into the reflector cup for 3 minutes but penetrates after 5 minutes, the closeness level is determined to be B; if the red ink does not penetrate into the reflector cup for 1 minute but penetrates after 3 minutes, the closeness level is determined to be C; if the red ink penetrates into the reflector cup within 1 minute, the closeness level is determined to be D; if the closeness level is D, it proves that the closeness between plastic and hardware is poor, which may cause the lamp bead to fail. On the contrary, if the closeness level is A, B, or C, the encapsulated lamp bead has excellent air tightness and good reliability.

[0154] Reflectivity: A test piece with a length of 60 mm, a width of 60 mm, and a thickness of 1 mm was prepared by injection molding of the PA6T / X composite material. The reflectivity of the test piece to light with a wavelength of 460 nm was measured using a Color Eye 7000A colorimeter and recorded as the initial reflectivity R1.

[0155] Yellowing resistance test: PA6T / X composite material was injection molded into a test piece with a length of 60mm, a width of 60mm and a thickness of 1mm. The test piece was then placed under a high temperature condition of 265°C for 7 minutes, and then cooled to room temperature, and repeated 3 times. The reflectivity of the aged test piece to 460nm wavelength light was measured with a Color Eye 7000A colorimeter, and recorded as the reflectivity after aging R2. The yellowing resistance is characterized by the difference between the initial reflectivity R1 and the reflectivity after aging R2.

[0156] ΔR460=R1-R2

[0157] Gas: When testing gas, a mold with a spiral exhaust port with a periphery of 0.5*10mm is provided for injection molding. According to standard injection molding conditions, each composition is injected 100 times, and then the blockage of the spiral exhaust port is evaluated by naked eye. If there is visible dirt, it means that the gas is unqualified.

[0158] Recycling times: The polyamide composition was made into an ISO standard specimen using an injection molding machine (Taichung Precision Machinery VS-80), and its initial tensile strength was first tested (according to ISO 527 test standard). Then all the specimens were broken, and then made into an ISO standard specimen to test its tensile strength. This process was repeated until the tensile strength of the specimen was lower than the initial tensile strength. The number of times the specimen was broken represents its recyclable number.

[0159] Number of blisters during reflow soldering: Provide a mold with a size of 21mm in length, 22mm in width, 1mm to 2mm in thickness, and 8 pieces in one mold. According to standard injection molding conditions, each composition was injected 30 times for a total of 200 samples. The wave reflow soldering temperature was 260℃ to 280℃, and the dwell time at 280℃ was more than 60 seconds. Check the number of blisters on the appearance of the product with the naked eye.

[0160] The performance test data of each embodiment and comparative example are shown in Table 4-Table 5.

[0161] Table 4

[0162]

[0163] Table 5

[0164]

[0165] With reference to Tables 1 to 5, in the polyamide composite materials prepared in Comparative Examples 1 to 4, the semi-aromatic polyamide resins used were PA6T / 66, PA6T / 610, PA6T / 612, and PA6T / 6I, respectively. No mercapto monocarboxylic acid was added during the preparation of the semi-aromatic polyamides in Comparative Examples 1 to 4, and the obtained semi-aromatic polyamides contained neither thioester groups nor mercapto groups. The polyamide composite materials prepared in Comparative Examples 1 to 4 had low moisture sensitivity levels, and their sealing levels and yellowing resistance were inferior to those of Examples 2 to 18.

[0166] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0167] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A semi-aromatic polyamide resin, characterized in that The raw materials for preparing the semi-aromatic polyamide resin include diamine, dicarboxylic acid and mercapto monocarboxylic acid; the dicarboxylic acid includes substituted or unsubstituted C 8~20 Aromatic dicarboxylic acids.

2. The semi-aromatic polyamide resin according to claim 1, wherein The diamine includes substituted or unsubstituted C 6~12 diamine; and / or The number of carbon atoms in the mercaptomonocarboxylic acid is 2 to 12; and / or The C 8~20 The aromatic dicarboxylic acid comprises at least one of phthalic acid, naphthalene dicarboxylic acid and biphenyl dicarboxylic acid; and / or The dicarboxylic acid also includes substituted or unsubstituted C 2~12 Aliphatic dicarboxylic acids.

3. The semi-aromatic polyamide resin according to claim 2, characterized in that The diamine includes 1,6-hexanediamine, or the diamine includes substituted or unsubstituted C 6~12 Branched diamines, substituted or unsubstituted C 7~12 At least one of the linear diamines and 1,6-hexanediamine; optionally, the diamines include at least one of 1,9-nonanediamine, 1,10-decanediamine, lauryl diamine, 1-4-butanediamine and 1,4-diaminocyclohexane and 1,6-hexanediamine.

4. The semi-aromatic polyamide resin according to claim 2, characterized in that The mercaptomonocarboxylic acid is selected from at least one of mercaptoacetic acid and mercaptopropionic acid; and / or, The dicarboxylic acid includes at least one of isophthalic acid, 1,4-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,2-biphenyl dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 1,10 sebacic acid, 1,12-dodecane dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid and diphenyl sulfone-4,4'-dicarboxylic acid, and terephthalic acid.

5. The semi-aromatic polyamide resin according to any one of claims 1 to 4, characterized in that Each of the substituted groups is independently selected from one of C1-C9 alkyl, amino, halogen, nitro, hydroxyl, thiol, carboxyl and cyano.

6. The semi-aromatic polyamide resin according to any one of claims 1 to 4, characterized in that: The molar ratio of the diamine, the dicarboxylic acid and the mercapto monocarboxylic acid is 1:1:(0.03-0.1).

7. A semi-aromatic polyamide resin, characterized in that Including the segment structure shown in formula (I): Formula (I); wherein R1 and R4 are each independently selected from substituted or unsubstituted C 6~18 Arylene or substituted or unsubstituted C 1~10 One of the alkylene groups, at least one of R1 and R4 is a substituted or unsubstituted C 6~18 Arylene; R2 is substituted or unsubstituted C1~ 12 Alkylene; R3 is substituted or unsubstituted C 1~11 of alkylene.

8. The semi-aromatic polyamide resin according to claim 7, wherein The semi-aromatic polyamide resin satisfies at least one of the following conditions: (1) R1 is p-phenyl or m-phenyl; (2) R2 is C6~C 12 Alkylene; (3) R3 is a C1~C3 alkylene group; (4) R4 is p-phenyl, m-phenyl or C 1~10 Alkylene.

9. A method for preparing a semi-aromatic polyamide resin, characterized in that: The steps include: The diamine, dicarboxylic acid and mercapto monocarboxylic acid are mixed and prepolymerized to prepare a prepolymer; the dicarboxylic acid includes substituted or unsubstituted C 8~20 Aromatic dicarboxylic acids; The prepolymer is subjected to a solid phase viscosity enhancement treatment to prepare the semi-aromatic polyamide resin.

10. The preparation method according to claim 9, characterized in that: The preparation method satisfies at least one of the following conditions: (1) The prepolymerization step comprises: Under the protection of inert gas, heat up to 160℃~200℃ at a rate of 3℃ / min~10℃ / min, and react at constant temperature for 30min~90min; then heat up to 250℃~300℃ at a rate of 1℃ / min~5℃ / min, and react at constant temperature for 3h~6h under stirring conditions of 70 rpm~100 rpm; (2) The conditions of the solid phase viscosity enhancement treatment include: temperature of 250°C to 280°C, vacuum degree of 20Pa to 60Pa, and time of 1.5h to 2h.

11. The preparation method according to any one of claims 9 to 10, characterized in that: The prepolymerization reaction is carried out under the action of a catalyst; The catalyst is selected from at least one of sulfuric acid, phosphorous acid, sodium phosphite and p-toluenesulfonic acid; and / or, The added amount of the catalyst is 0.1% to 0.5% of the total mass of the diamine, the dicarboxylic acid and the mercapto monocarboxylic acid.

12. A semi-aromatic polyamide composite material, characterized in that: Calculated by mass, it includes the following components: 40 to 70 parts of the semi-aromatic polyamide resin according to any one of claims 1 to 8 or the semi-aromatic polyamide resin prepared by the preparation method according to any one of claims 9 to 11, 5 to 30 parts of reinforcing filler, 5 to 50 parts of white pigment and 0 to 5 parts of additives.

13. The semi-aromatic polyamide composite material according to claim 12, characterized in that: The semi-aromatic polyamide composite material satisfies at least one of the following conditions: (1) The reinforcing filler comprises wollastonite fibers; the average diameter of the wollastonite fibers is 1 μm to 25 μm, and the average length is 10 μm to 250 μm; (2) The white pigment includes titanium dioxide; (3) The additive includes at least one of an antioxidant, a whitening agent and a lubricant; the antioxidant is selected from a phenolic antioxidant or an amine antioxidant; the whitening agent is selected from at least one of magnesium oxide, zinc oxide and calcium oxide; the lubricant is selected from at least one of calcium stearate, zinc stearate, OP wax and PE wax.

14. A method for preparing a semi-aromatic polyamide composite material, characterized in that: The following steps are involved: Providing raw materials according to the components of the semi-aromatic polyamide composite material according to any one of claims 12 to 13; The raw materials are mixed and extruded to obtain the semi-aromatic polyamide composite material.

15. Use of the semi-aromatic polyamide composite material according to any one of claims 12 to 13 in the preparation of polyamide products.

16. A packaging film, characterized in that: It comprises the semi-aromatic polyamide composite material as described in any one of claims 12 to 13.

17. An LED lamp, characterized in that: It comprises a chip, a bracket and the packaging film as claimed in claim 16, wherein the chip is arranged on the bracket and the packaging film covers the chip.

18. An electronic device, characterized in that: Comprising the LED lamp as claimed in claim 17.

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