CN102108192B - Polyester-containing material, preparation method thereof and vehicle lamp combined decorating frame product - Google Patents
Polyester-containing material, preparation method thereof and vehicle lamp combined decorating frame product Download PDFInfo
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- CN102108192B CN102108192B CN2009102525709A CN200910252570A CN102108192B CN 102108192 B CN102108192 B CN 102108192B CN 2009102525709 A CN2009102525709 A CN 2009102525709A CN 200910252570 A CN200910252570 A CN 200910252570A CN 102108192 B CN102108192 B CN 102108192B
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Abstract
The invention provides a polyester-containing material. The material is a product which is prepared by mixing a mixture and polyester in a molten state. The mixture contains the polyester, a filler, polypropylene of which the number-average molecular weight is 2,000 to 15,000, a nucleating agent, a toughening agent and an ester exchange inhibitor, wherein the ester exchange inhibitor is selected from one or more of sodium pyrophosphate, triphenyl phosphate and calcium phosphate; the polyester is polyethylene glycol terephthalate and polybutylene terephthalate; and the filler is hollow ceramic microspheres and/or hollow glass microspheres. The invention also provides a method for preparing the polyester-containing material. A product prepared from the polyester-containing material provided by the invention has high rigidity, shock resistance, high-temperature resistance and weather resistance and good surface effect, can be directly metallized through vacuum aluminum coating without spraying a primer, has low cost and is environmentally-friendly.
Description
Technical field
The automobile lamp combination escutcheon product that the invention relates to a kind of material and this preparation methods and make by this material; More particularly, the automobile lamp combination escutcheon product that the invention relates to a kind of material that contains polyester and preparation method thereof and make by this material.
Background technology
Automobile lamp combination escutcheon product adopts heat-resisting PC (polycarbonate) material to make in the past always, substitutes and be used the material that PET (polyethylene terephthalate)/PBT (polybutylene terephthalate) and mineral-filled thing make in recent years gradually.
For example; CN1193568A discloses a kind of thermoplastic resin molded article; These goods comprise a kind of thermoplastic resin composition, and it comprises (A) polybutylene terephthalate resin, (B) pet resin; (C) (methyl) vinyl resin, (D) multilayer structure polymer particle and (E) mineral filler.
Compare characteristics such as the material that adopts PBT (polybutylene terephthalate)/PET (polyethylene terephthalate) and mineral-filled thing to make has the thermotolerance height, processibility is good and with low cost with heat-resisting PC material.But, need to adopt vacuum aluminum-coated method that the product that is made by this material is carried out metalized.Owing to the surface finish of the product that is made by material is not high; Cause defectives such as product surface is rough, glossiness is low, metal sense difference if directly carry out vacuum aluminum-coated meeting; And bad phenomenon such as bubble, bubble might appear, therefore, and before aluminizing; Need be at its surface spraying one deck priming paint improving its surface property, thus make the mirror effect of vapor deposition be able to represent.Although the method through adopting spraying priming paint can obtain effect coating preferably; But; The shock resistance of the product that is made by this material is not satisfactory, also can bring simultaneously as cost increase, increase, the product processes link of PT of unit product are complicated, production efficiency reduces, fraction defective increases and be prone to cause problem such as environmental pollution owing to the priming paint solvent evaporates.
Goal of the invention
The objective of the invention is in order to overcome relatively poor by the shock resistance of the product of the material prepn that contains polyester of prior art for preparing; Get final product direct metallized and provide a kind of material that contains polyester and preparation method thereof, the feasible product that makes by this material to have preferable shock resistance and need not to spray priming paint.
The invention provides a kind of material that contains polyester; This material is through mixing under the molten state of polyester and product that form by a kind of mixture; Wherein, It is Vestolen PP 7052, nucleator, toughner and the ester exchange inhibitor of 2000-15000 that said mixture contains polyester, filler, number-average molecular weight; Said ester exchange inhibitor is selected from one or more in trisodium phosphate, triphenyl phosphite and the calcium phosphate, and said polyester is polyethylene terephthalate and polybutylene terephthalate, and said filler is hollow ceramic microballon and/or hollow glass microbead.
The present invention also provides a kind of preparation methods that contains polyester; Wherein, This method comprises that polyester, filler, number-average molecular weight are that Vestolen PP 7052, nucleator, toughner and the ester exchange inhibitor of 2000-15000 mixed the mixture that obtains is mixing under the molten state of polyester; And with the products therefrom extruding pelletization, said ester exchange inhibitor is selected from one or more in trisodium phosphate, triphenyl phosphite and the calcium phosphate; Said polyester is ethylene glycol terephthalate and polybutylene terephthalate; Said filler is hollow ceramic microballon and/or hollow glass microbead.
The present invention also provides a kind of automobile lamp combination escutcheon product, and this product is made by the material that contains polyester, and wherein, the said material that contains polyester is the material that contains polyester provided by the invention.
Compare with the material that mineral-filled thing makes with adopting PET (polyethylene terephthalate)/PBT (polybutylene terephthalate); Rigidity height, shock resistance, the resistance to elevated temperatures of the product that makes by the material that contains polyester provided by the invention and having excellent weather resistance; And surface effect is good; And can spray priming paint and directly the goods that made by this material are carried out vacuum aluminum-coated metallization, and cost is lower, and environmentally friendly.The material that contains polyester provided by the invention can satisfy the processing conditions and the request for utilization of automobile lamp combination escutcheon, is particularly useful for making automobile lamp combination escutcheon product.
Embodiment
According to the present invention; The said material that contains polyester is through mixing under the molten state of polyester and product that form by a kind of mixture; Wherein, It is Vestolen PP 7052, nucleator, inhibitor, toughner and the ester exchange inhibitor of 2000-15000 that said mixture contains polyester, filler, number-average molecular weight; Said ester exchange inhibitor is selected from one or more in trisodium phosphate, triphenyl phosphite and the calcium phosphate, and said polyester is polyethylene terephthalate and polybutylene terephthalate, and said filler is hollow ceramic microballon and/or hollow glass microbead.
Wherein, the specific density of said polybutylene terephthalate (PBT) is the 1.30-1.35 gram per centimeter
3, fusing point is 230-260 ℃, relative viscosity is 0.6-1.0PS; The specific density of said polyethylene terephthalate (PET) is the 1.35-1.38 gram per centimeter
3, fusing point is 250-260 ℃, relative viscosity 0.6-1.2PS.
According to the present invention; The adding of said ester exchange inhibitor; Particularly the adding of trisodium phosphate can reach the transesterify inhibition well and promote the crystalline synergy; Avoided the random copolymers of polyester blend generation mechanical property poor-performing, thus the rigidity and the surface luster of having improved resin itself.
According to the present invention, the adjustable extent broad of each components contents in the said mixture is in order further to optimize the performance of the material that contains polyester that obtains; Can effectively improve crystallization velocity and the percent crystallinity of PET as the content of the content of the PET of matrix resin and PBT and nucleator through suitable adjustment; Thereby improved the rigidity and the characteristics such as thermotolerance and profile pattern of resin itself, and reduced production costs, therefore; Under the preferable case; Gross weight with this mixture is a benchmark, and the content of said polyethylene terephthalate can be 40-60 weight %, more preferably 43-56 weight %; The content of said polybutylene terephthalate can be 5-30 weight %, more preferably 10-30 weight %; The content of said filler can be 5-20 weight %, more preferably 10-20 weight %; Said number-average molecular weight is that the polyacrylic content of 2000-15000 can be 0.5-2 weight %, more preferably 0.6-1.2 weight %; The content of said nucleator can be 0.2-2 weight %, more preferably 0.5-1.5 weight %; The content of said toughner can be 3-10 weight %, more preferably 4-10 weight %; The content of said ester exchange inhibitor can be 0.2-2 weight, more preferably 0.2-1 weight %.
According to the present invention, said nucleator can be preferably Sorbitol dibenzal and/or Sodium Benzoate for the conventional various nucleators in this area.More preferably under the situation,, can further guarantee to improve crystallization velocity and the percent crystallinity of PET with Sorbitol dibenzal and the composite use of Sodium Benzoate; The adjustable extent broad of the ratio of said Sorbitol dibenzal and Sodium Benzoate, under the preferable case, the weight ratio of said Sorbitol dibenzal and Sodium Benzoate can be 1.5-2.5: 1.
Promote nucleation in order better to suppress transesterification reaction and to form synergy with nucleator, the weight ratio of said nucleator and ester exchange inhibitor can be 1.5-2.5: 1.
According to the present invention; Said toughner can be the conventional various toughner in this area; Under the preferable case; Said toughner is maleic anhydride grafted polyethylene octene elastomer (POE) (its percentage of grafting is generally 0.8-1.2 weight %) and/or ethylene-acrylate-SY-Monomer G (wherein, acrylate content is 22-28 weight %, SY-Monomer G content 6.5-9 weight %).The adding of crystalline refinement and toughner can obviously improve the shock strength that contains polyester material, owing to the raising of impact property has significantly reduced material rimose probability.
Said filler can be the particle of hollow ceramic microballon and/or hollow glass microbead; The selectable range broad of the particle diameter of hollow ceramic microballon and/or hollow glass microbead; In order further to play the enhanced effect, said hollow ceramic microballon and/or hollow glass microbead particulate D
50Be preferably the 5-15 micron.
Under the preferable case, said mixture can also contain one or more materials that are selected from inhibitor, coupling agent and the photostabilizer; Said inhibitor is selected from one or more in phenolic compound, amine compound, organosulfur compound and the bi-ester of phosphite; Said coupling agent is silane coupling agent and/or aluminate coupling agent; Said photostabilizer is selected from one or more in amine compound, azimidobenzene, the benzophenone compounds.The addition of said each material can be the addition of routine; As; Gross weight with said mixture is a benchmark, and the content of said polyethylene terephthalate can be 40-60 weight %, and the content of said polybutylene terephthalate can be 5-30 weight %; The content of said filler can be 5-20 weight %; Said number-average molecular weight is that the polyacrylic content of 2000-15000 can be 0.5-2 weight %, and the content of said nucleator can be 0.2-2 weight %, and the content of said toughner can be 3-10 weight %; The content of said ester exchange inhibitor can be 0.2-2 weight %, and the said content that is selected from one or more materials in inhibitor, coupling agent and the photostabilizer can be 0.1-5 weight %.
Under the preferable case, the content of said inhibitor can be 0.2-1 weight %, and the content of said coupling agent can be 0.2-2 weight %, and the content of said photostabilizer can be 0.1-2 weight %.
Said inhibitor can be the conventional various inhibitors in this area; For example, said inhibitor can be selected from one or more in phenolic antioxidant (like antioxidant 1010,1076 etc.), amine type inhibitor (like antioxidant A etc.), organic sulfur type antioxidant (like anti-oxidant DLTP etc.) and the phosphite type inhibitor (like oxidation inhibitor 168 or DSTP etc.).
Said coupling agent can be the various silane coupling agents and/or the aluminate coupling agent of routine; For example, said silane coupling agent can be selected from one or more in propenyl diethoxy silane, vinyltriethoxysilane, vinyltrimethoxy silane, mercaptopropyl trimethoxysilane, r-glycidyl ether oxygen propyl trimethoxy silicane, propyl methacrylate base Trimethoxy silane and the aminopropyl triethoxysilane; Said aluminate coupling agent can be DL-411 type or DL-451 type aluminate coupling agent.
After adding coupling agent, make through the hollow ceramic microballon of coupling processing and/or the existence of hollow glass microbead and obviously improved the melting index of material, thereby improved its injection moulding processing characteristics; Improved the rigidity of material, the density that has reduced material has alleviated material weight, has improved the wear resistance of material simultaneously; Increase heat-resisting, the heat-proof quality of material, thereby prolonged other non-refractory material be close to the product that obtains by this material such as the work-ing life of plastics; Improved the surface finish of material.
In order to prevent and to suppress material in the course of processing or in the use,, can add photostabilizer because factors such as light, heat cause too early degraded.Said photostabilizer can be selected from one or more in amine type photostabilizer, azimidobenzene, the benzophenone compounds.As, the trade mark that can be selected from UV-series product such as Alpha-hydroxy-4-oxy-octyl benzophenone (being called for short UV531) and the production of vapour Bagong department is the photostabilizer of Tinuvin234.
According to the present invention; The said preparation methods that contains polyester comprises that polyester, filler, number-average molecular weight are that Vestolen PP 7052, nucleator, toughner and the ester exchange inhibitor of 2000-15000 mixed the mixture that obtains is mixing under the molten state of polyester; And with the products therefrom extruding pelletization, said ester exchange inhibitor is selected from one or more in trisodium phosphate, triphenyl phosphite and the calcium phosphate; Said polyester is ethylene glycol terephthalate and polybutylene terephthalate; Said filler is hollow ceramic microballon and/or hollow glass microbead.
According to the present invention, be benchmark with the gross weight of this mixture, the consumption of each material makes the content of polyethylene terephthalate in the mixture can be 40-60 weight %, more preferably 43-56 weight %; The content of polybutylene terephthalate can be 5-30 weight %, more preferably 10-30 weight %; The content of filler can be 5-20 weight %, more preferably 10-20 weight %; Molecular weight is that the polyacrylic content of 2000-15000 can be 0.5-2 weight %, more preferably 0.6-1.5 weight %; The content of nucleator can be 0.2-2 weight %, more preferably 0.5-1.5 weight %; The content of toughner can be 3-10 weight %, more preferably 4-10 weight %; The content of ester exchange inhibitor can be 0.2-2 weight, more preferably 0.2-1 weight %.
Under the preferable case; This method also comprises polyester, filler, number-average molecular weight, and to be Vestolen PP 7052, nucleator, toughner and the ester exchange inhibitor of 2000-15000 mix with one or more materials in being selected from inhibitor, coupling agent and photostabilizer; Gross weight with this mixture is a benchmark; It is 40-60 weight % that the consumption of each material makes the content of polyethylene terephthalate in the mixture, and the content of polybutylene terephthalate is 5-30 weight %, and the content of filler is 5-20 weight %; Number-average molecular weight is that the polyacrylic content of 2000-15000 is 0.5-2 weight %; The content of nucleator is 0.2-2 weight %, and the content of toughner is 3-10 weight %, and the content of ester exchange inhibitor is 0.2-2 weight; The content that is selected from one or more materials in inhibitor, coupling agent and the photostabilizer is 0.1-5 weight %.
Under the preferable case, the content of said inhibitor can be 0.2-1 weight %, and the content of said coupling agent can be 0.2-2 weight %, and the content of said photostabilizer can be 0.1-2 weight %.
According to method of the present invention; With polyester, filler, number-average molecular weight is that one or more materials in inhibitor, coupling agent and the photostabilizer of being selected from that Vestolen PP 7052, nucleator, toughner and ester exchange inhibitor and the selectivity of 2000-15000 contains mix the mixture mixing process under the molten state of polyester that obtains and can carry out in the various device known in the art; As; At mixing facilities; Like mixed melting in Banbury mixer or the mill; Also can be in twin screw extruder mixed melting, preferably also be included in mixing facilities or the twin screw extruder process with gained melts extruding pelletization, be conventionally known to one of skill in the art with method, condition and the equipment used of mixture extruding pelletization.
With polyester, filler, number-average molecular weight is that one or more materials in inhibitor, coupling agent and the photostabilizer of being selected from that Vestolen PP 7052, nucleator, toughner and ester exchange inhibitor and the selectivity of 2000-15000 contains mix the mixture that obtains under the molten state of polyester when mixing; The temperature of the molten state of said polyester is preferably 250-260 ℃ for being not less than 250 ℃ at least; Not special qualification of mixing time as long as guarantee polyester is in molten state, and gets final product with the abundant mixing of other raw material, and generally, the said mixing time can be 5-40 minute, is preferably 10-30 minute.
Containing polyester, filler, number-average molecular weight and be Vestolen PP 7052, nucleator, toughner and the ester exchange inhibitor of 2000-15000 and the preparation process of mixture that is selected from one or more materials in inhibitor, coupling agent and the photostabilizer that selectivity contains can adopt and well known to a person skilled in the art the whole bag of tricks; And the addition sequence of each material is to the not influence of character of the mixture that obtains; As; Each component mixed obtain mixture, preferably evenly obtain this mixture in stirrer for mixing.Stirring condition and method are conventionally known to one of skill in the art, and those skilled in the art's instruction according to the present invention is easy to select suitable agitation condition and method.
According to an embodiment of the present invention, said preparing method's concrete steps are following:
(1) be that to join high-speed mixer and mixing even for one or more materials in inhibitor, coupling agent and the photostabilizer of being selected from of containing of Vestolen PP 7052, nucleator, toughner and ester exchange inhibitor and the selectivity of 2000-15000 with polyester, filler, number-average molecular weight; Obtain mixture; Wherein, The temperature and time of blended under agitation is conventionally known to one of skill in the art, and for example, the temperature of blended under agitation can be 60-80 ℃; The time of blended under agitation can be 1-30 minute, and the rotating speed of blended under agitation can be 200-2500 rev/min; Under the preferable case, under 800-1200 rev/min rotating speed, add earlier coupling agent and filler stirring 2-10 minute, and then add other component and under 1500-2000 rev/min rotating speed, stir and obtained mixture in 5-10 minute.
(2) mixture that obtains is mixing under the molten state of polyester, extruding pelletization.Wherein, said step mixing, extruding pelletization can be carried out in Banbury mixer or mill, extrude and be ground into particle 250-260 ℃ of following melting mixing; Also can in twin screw extruder, carry out, be 32 in length-to-diameter ratio: 1-52: 1, and screw speed 100-280 rev/min; Said twin screw extruder generally is divided into 5 sections from the feed end to the discharge end; From the feed end to the discharge end; Each zone temperatures is set at 250-255 ℃, 250-255 ℃, 250-255 ℃, 255-260 ℃, 255-260 ℃ respectively successively, and the vacuum tightness of each section is to mix and extruding pelletization under the condition of 0.02 to 0.09 MPa.Vacuum tightness in this specification sheets is meant the absolute value (absolute pressure is less than barometric point) of the difference of absolute pressure and barometric point.
The material that contains polyester provided by the invention can be applied to various fields, like fields such as automobile, electronics, electrical equipment, space materials, is particularly useful for making automobile lamp combination escutcheon product.Can adopt the method for various routines well known in the art by the method for the material prepn automobile lamp combination escutcheon product that contains polyester, the method for injection moulding for example, its condition of molding can be the injection moulding condition of routine well known in the art.The more important thing is; The goods that adopt the material that contains polyester provided by the invention to make can spray priming paint and directly these goods carried out vacuum aluminum-coated metallization; Rigidity height, shock resistance, the resistance to elevated temperatures of the product that finally makes and having excellent weather resistance, and surface effect is good.
To be explained in further detail the present invention through specific embodiment below.
Toughner among the following embodiment is that maleic anhydride graft POE (Vilaterm octene elastomer) (percentage of grafting is generally 0.8-1.2 weight %) clings to chemical industry available from the Nanjing moral, and the trade mark is POE-G-1; Available from French Arkema, the trade mark is AX8900 to ethylene-acrylate-SY-Monomer G (acrylate content is generally 22-28 weight %, the general 6.5-9 weight of SY-Monomer G content %); The specific density of polyethylene terephthalate (PET) is 1.35 gram per centimeters
3, fusing point is 250 ℃, relative viscosity 1.0PS; The specific density of polybutylene terephthalate (PBT) is 1.3 gram per centimeters
3, fusing point is 240 ℃, relative viscosity is 0.8PS.
Embodiment 1
Present embodiment is used to explain the preparation of the material that contains polyester provided by the invention and the preparation of automobile lamp combination escutcheon product.
Under 60 ℃, with 0.4 weight part DL-411 type aluminate coupling agent, 10 weight part hollow ceramic microballon (D
50Be 5 microns) join in the high mixer; Under 800 rev/mins rotating speed, stirred 5 minutes, add 53.5 weight part polyethylene terephthalates (PET) then, 30 weight part polybutylene terephthalates (PBT); 4 weight part toughner ethylene-acrylate-SY-Monomer Gs; 0.6 the parts by weight average molecular weight is 3000 Vestolen PP 7052,0.3 weight part nucleator Sorbitol dibenzal and 0.2 weight part nucleator Sodium Benzoate, 0.2 weight part primary antioxidant 1010; 0.1 weight part auxiliary antioxidant 168; 0.2 weight part ester exchange inhibitor trisodium phosphate and 0.5 weight part photostabilizer Tinuvin234 stirred 10 minutes under 1500 rev/mins rotating speed, obtained mixture;
The mixture that step (1) obtains is sent in the twin screw compounding forcing machine (SJSH-30 type, Nanjing Rubber-Plastic Machinery Plant) the length-to-diameter ratio L of forcing machine: D=36: 1, screw diameter is 53 millimeters of Φ.The rotating speed of screw rod is adjusted to 400 rev/mins, from the feed end to the discharge end, is divided into 5 sections, each zone temperatures is controlled at respectively: 250 ℃; 255 ℃, 250 ℃, 260 ℃, 260 ℃; The vacuum tightness of each section remains 0.05 to 0.08 MPa; Under these conditions, through melt extruding granulation, obtain containing the material J1 of polyester;
260 ℃ of following injection mouldings, then, directly aluminize at the moulded products surface vacuum (thickness of coating is 120 nanometers) obtains automobile lamp combination escutcheon products C 1 with the above-mentioned material that contains polyester that obtains.
Embodiment 2
Present embodiment is used to explain the preparation of the material that contains polyester provided by the invention and the preparation of automobile lamp combination escutcheon product.
Under 80 ℃, with 0.3 weight part silane coupling agent vinyl triethoxy and 10 weight part hollow ceramic microballon (D
50Be 5 microns) and 10 weight part hollow glass microbead (D
50Be 5 microns), join in the high mixer, under 600 rev/mins rotating speed, stirred 5 minutes; Add 43 weight part polyethylene terephthalates (PET) then; 28 weight part polybutylene terephthalates (PBT), 6 weight part toughner ethylene-acrylate-SY-Monomer Gs, 0.8 weight part molecular weight are 4000 Vestolen PP 7052; 0.5 weight part nucleator Sorbitol dibenzal and 0.2 weight part nucleator Sodium Benzoate; 0.2 weight part primary antioxidant 1010,0.15 weight part auxiliary antioxidants, 168,0.45 weight part ester exchange inhibitor trisodium phosphates and 0.4 weight part photostabilizer Tinuvin 234; Under 1200 rev/mins rotating speed, stirred 10 minutes, obtain mixture;
The above-mentioned mixture that obtains is sent in the twin screw compounding forcing machine (SJSH-30 type, Nanjing Rubber-Plastic Machinery Plant), and the condition according to embodiment 1 melt extrudes granulation with mixture, obtains containing the material J2 of polyester; Method according to embodiment 1 adopts the material J2 that contains polyester to prepare automobile lamp combination escutcheon products C 2.
Embodiment 3
Present embodiment is used to explain the preparation of the material that contains polyester provided by the invention and the preparation of automobile lamp combination escutcheon product.
Method according to embodiment 1 prepares mixture, and different is, directly all raw materials is inserted in the high mixer together, under 800 rev/mins rotating speed, stirs 15 minutes, obtains mixture;
The above-mentioned mixture that obtains is sent in the twin screw compounding forcing machine (SJSH-30 type, Nanjing Rubber-Plastic Machinery Plant), and the condition according to embodiment 1 melt extrudes granulation with mixture, obtains containing the material J3 of polyester; Method according to embodiment 1 adopts the material J3 that contains polyester to prepare automobile lamp combination escutcheon products C 3.
Embodiment 4
Present embodiment is used to explain the preparation of the material that contains polyester provided by the invention and the preparation of automobile lamp combination escutcheon product.
Under 70 ℃, with 0.8 weight part silane coupling agent vinyl triethoxyl silane, 15 weight part hollow glass microbead (D
50Be 8 microns), join in the high mixer, under 750 rev/mins rotating speed, stirred 5 minutes; Add 60 weight part polyethylene terephthalates (PET) then; 10 weight part polybutylene terephthalates (PBT), 8 weight part toughner ethylene-acrylate-SY-Monomer Gs and 2 weight part maleic anhydride graft POE, 1 weight part molecular weight is 4500 Vestolen PP 7052; 1 weight part nucleator Sorbitol dibenzal and 0.5 weight part nucleator Sodium Benzoate; 0.4 weight part primary antioxidant 1010,0.3 weight part auxiliary antioxidants, 168,0.5 weight part ester exchange inhibitor trisodium phosphates and 0.5 weight part triphenyl phosphite; Under 1200 rev/mins rotating speed, stirred 10 minutes, obtain mixture;
The above-mentioned mixture that obtains is sent in the twin screw compounding forcing machine (SJSH-30 type, Nanjing Rubber-Plastic Machinery Plant), and the condition according to embodiment 1 melt extrudes granulation with mixture, obtains containing the material J4 of polyester; Method according to embodiment 1 adopts the material J4 that contains polyester to prepare automobile lamp combination escutcheon products C 4.
Embodiment 5
Present embodiment is used to explain the preparation of the material that contains polyester provided by the invention and the preparation of automobile lamp combination escutcheon product.
Under 70 ℃, with 54 weight part polyethylene terephthalates (PET), 20 weight part polybutylene terephthalates (PBT), 3.2 weight part toughner ethylene-acrylate-SY-Monomer Gs, 19 weight part hollow glass microbead (D
50Be 8 microns), 1.5 weight part molecular weight are 4500 Vestolen PP 7052,1 weight part nucleator Sorbitol dibenzal and 0.5 weight part nucleator Sodium Benzoate; 0.8 weight part ester exchange inhibitor trisodium phosphate; Add in the high mixer, under 1200 rev/mins rotating speed, stirred 15 minutes, obtain mixture;
The above-mentioned mixture that obtains is sent in the twin screw compounding forcing machine (SJSH-30 type, Nanjing Rubber-Plastic Machinery Plant), and the condition according to embodiment 1 melt extrudes granulation with mixture, obtains containing the material J5 of polyester; Method according to embodiment 1 adopts the material J5 that contains polyester to prepare automobile lamp combination escutcheon products C 5.
Embodiment 6
Present embodiment is used to explain the preparation of the material that contains polyester provided by the invention and the preparation of automobile lamp combination escutcheon product.
Method according to embodiment 1 prepares mixture, and different is that nucleator is 0.5 weight part Sorbitol dibenzal.
The gained mixture is sent in the twin screw compounding forcing machine (SJSH-30 type, Nanjing Rubber-Plastic Machinery Plant), and the condition according to embodiment 1 melt extrudes granulation with mixture, obtains containing the material J6 of polyester;
Method according to embodiment 1 adopts the material J6 that contains polyester to prepare automobile lamp combination escutcheon products C 6.
Embodiment 7
Present embodiment is used to explain the preparation of the material that contains polyester provided by the invention and the preparation of automobile lamp combination escutcheon product.
Method according to embodiment 1 prepares mixture, and different is that nucleator is 0.1 weight part Sorbitol dibenzal and 0.2 weight part nucleator Sodium Benzoate; Said transesterify agent is 0.4 weight part trisodium phosphate;
The mixture that obtains is sent in the twin screw compounding forcing machine (SJSH-30 type, Nanjing Rubber-Plastic Machinery Plant), and the condition according to embodiment 1 melt extrudes granulation with mixture, obtains containing the material J7 of polyester; Method according to embodiment 1 adopts the material J7 that contains polyester to prepare automobile lamp combination escutcheon products C 7.
Embodiment 8
Present embodiment is used to explain the preparation of the material that contains polyester provided by the invention and the preparation of automobile lamp combination escutcheon product.
Under 65 ℃, with 0.15 weight part silane coupling agent vinyl triethoxyl silane, 0.15 weight part DL-451 type aluminate coupling agent, 18 weight part hollow glass microbead (D
50Be 8 microns), join the high mixer kind, under 800 rev/mins rotating speed, stirred 5 minutes; Add 45 weight part polyethylene terephthalates (PET) then, 30 weight part polybutylene terephthalates (PBT), 5 weight part toughner ethylene-acrylate-SY-Monomer Gs; 0.6 the weight part molecular weight is 3500 Vestolen PP 7052,0.3 weight part nucleator Sorbitol dibenzal and 0.2 weight part nucleator Sodium Benzoate, 0.2 weight part primary antioxidant 1010; 0.1 weight part auxiliary antioxidant 168; 0.3 weight part ester exchange inhibitor trisodium phosphate stirred 10 minutes under 1200 rev/mins rotating speed, obtained mixture;
The above-mentioned mixture that obtains is sent in the twin screw compounding forcing machine (SJSH-30 type, Nanjing Rubber-Plastic Machinery Plant), and the condition according to embodiment 1 melt extrudes granulation with mixture, obtains containing the material J8 of polyester; Method according to embodiment 1 adopts the material J8 that contains polyester to prepare automobile lamp combination escutcheon products C 8.
Comparative Examples 1
This Comparative Examples is used to explain preparation and the preparation of automobile lamp combination escutcheon product of the material that contains polyester of prior art.
With 50 weight part polybutylene terephthalates (PBT), 29.5 weight part polyethylene terephthalates (PET), 20 weight part talcum powder or wollastonites; 0.5 weight part antioxidant 1010; Join in the high mixer, under 800 rev/mins rotating speed, stirred 10 minutes, obtain mixture; The above-mentioned mixture that obtains is sent into twin screw compounding forcing machine (SJSH-30 type; Nanjing Rubber-Plastic Machinery Plant) in; Condition according to embodiment 1; Mixture is melt extruded granulation, obtain containing the material of polyester, obtaining with the polyester material through injection moulding is the automobile lamp combination escutcheon product J J1 of matrix again;
With 49 gram thermoplastic acrylic resins, H type NC1/4s Nitrocellulose 3 grams, DOP 1.5 grams, Witcizer 300 1.0 grams and dioctyl sebacate 1.0 gram softening agent, EFKA37772.5 gram flow agent, 1.5 gram anti-settling agents (DS6500/6800-20X of U.S. TAVY), 1 wetting dispersing agent Kerper-602 and YLENE 15 grams, butylacetate 15 grams, butyl glycol ether 10 grams and propyl carbinol 10 gram mixing diluents, be stirred to abundant dissolving; With adding silver slurry 5660NS 12.5 grams in this mixture, stir; The slurries that filtration obtains to remove residue wherein, obtain priming paint;
Above-mentioned priming paint is sprayed on the material shell of moulding, at 50 ℃ of oven dry spraying ultraviolet light polymerization varnish after 15 minutes, and through UV-irradiation 25 seconds, obtains thickness and be 5 microns solidifying film layer;
And carry out the vacuum aluminum-coated automobile lamp for preparing according to the method for embodiment 1 at this product surface that is coated with priming paint and make up escutcheon products C C1.
Embodiment 9-16
This embodiment is used to explain the performance test of the material that contains polyester.
The material that contains polyester that will be made by embodiment 1-8 is at 260 ℃ of following injection moulding standard bars, and measures the character of the material that contains polyester according to criterion.
The melting index that adopts ASTMD1238 to measure;
Adopt ASTMD638 to measure tensile strength;
Adopt ASTMD790 to measure flexural strength and modulus in flexure;
Adopt ASTMD256 to measure the Izod shock strength;
Adopt ASTMD648 to measure heat-drawn wire;
Adopt ASTMD792 to measure density;
The result is as shown in table 1.
Comparative Examples 2
This Comparative Examples is used to explain the performance test of the material that contains polyester.
Adopt the method identical with embodiment 9-16 to test, different is, test be the material that makes by Comparative Examples 1.The result is as shown in table 1.
Table 1
| The embodiment numbering | Material number | Melting index (g/10min) | Tensile strength (MPa) | Flexural strength (MPa) | Modulus in flexure (MPa) | Shock strength (J/m) | Heat-drawn wire (℃) | Density (g/cm 3) |
| Embodiment 9 | J1 | 17 | 64 | 92 | 3880 | 76 | 188 | 1.29 |
| Embodiment 10 | J2 | 18 | 64 | 90 | 3900 | 76 | 188 | 1.25 |
| Embodiment 11 | J3 | 18 | 59 | 85 | 3500 | 62 | 182 | 1.25 |
| Embodiment 12 | J4 | 18 | 61 | 89 | 3820 | 75 | 187 | 1.26 |
| Embodiment 13 | J5 | 17.5 | 56 | 82 | 3400 | 58 | 180 | 1.26 |
| Embodiment 14 | J6 | 18 | 60 | 86 | 3650 | 70 | 185 | 1.26 |
| Embodiment 15 | J7 | 18 | 62.5 | 88 | 3680 | 72 | 186 | 1.26 |
| Embodiment 16 | J8 | 18 | 62 | 90 | 3850 | 75 | 189 | 1.26 |
| Comparative Examples 2 | JJ1 | 12 | 55 | 88 | 3300 | 25 | 175 | 1.48 |
Data from last table 1 can be found out; Compare with the material that mineral-filled thing makes with adopting PBT (polybutylene terephthalate)/PET (polyethylene terephthalate); The melting index that contains the material of polyester of the present invention obviously increases, and makes that the performance of machine-shaping is better.And the shock resistance that contains the material of polyester of the present invention significantly improves, and greatly reduces the cracking rate of product, has resistance to elevated temperatures simultaneously and has excellent weather resistance.In addition, the density of material also decreases, and can alleviate the weight of car body.And the surface effect of product is good, and can spray priming paint and directly the goods that made by this material are carried out vacuum aluminum-coated metallization, and yield rate reaches more than 99.3%, and cost is lower.
Claims (10)
1. material that contains polyester; This material is through mixing under the molten state of polyester and product that form by a kind of mixture; It is characterized in that; It is Vestolen PP 7052, nucleator, toughner and the ester exchange inhibitor of 2000-15000 that said mixture contains polyester, filler, number-average molecular weight; Said ester exchange inhibitor is selected from one or more in trisodium phosphate, triphenyl phosphite and the calcium phosphate, and said polyester is polyethylene terephthalate and polybutylene terephthalate, and said filler is hollow ceramic microballon and/or hollow glass microbead; And the gross weight with said mixture is a benchmark; The content of said polyethylene terephthalate is 40-60 weight %, and the content of said polybutylene terephthalate is 5-30 weight %, and the content of said filler is 5-20 weight %; Said number-average molecular weight is that the polyacrylic content of 2000-15000 is 0.5-2 weight %; The content of said nucleator is 0.2-2 weight %, and the content of said toughner is 3-10 weight %, and the content of said ester exchange inhibitor is 0.2-2 weight %.
2. material according to claim 1, wherein, said nucleator is Sorbitol dibenzal and/or Sodium Benzoate; Said toughner is maleic anhydride grafted polyethylene octene elastomer and/or ethylene-acrylate-SY-Monomer G; Said hollow ceramic microballon and/or hollow glass microbead particulate D
50Be the 5-15 micron.
3. material according to claim 1, wherein, said nucleator is the mixture of Sorbitol dibenzal and Sodium Benzoate, the weight ratio of Sorbitol dibenzal and Sodium Benzoate is 1.5-2.5:1; The weight ratio of said nucleator and ester exchange inhibitor is 1.5-2.5:1.
4. material according to claim 1, wherein, said mixture also contains one or more materials that are selected from inhibitor, coupling agent and the photostabilizer; Said inhibitor is selected from one or more in phenolic antioxidant, amine type inhibitor, organic sulfur type antioxidant and the phosphite type inhibitor; Said coupling agent is silane coupling agent and/or aluminate coupling agent; Said photostabilizer is selected from one or more in amine type photostabilizer, azimidobenzene, the benzophenone compounds.
5. material according to claim 4 wherein, is a benchmark with the gross weight of this mixture; The content of said polyethylene terephthalate is 40-60 weight %; The content of said polybutylene terephthalate is 5-30 weight %, and the content of said filler is 5-20 weight %, and said number-average molecular weight is that the polyacrylic content of 2000-15000 is 0.5-2 weight %; The content of said nucleator is 0.2-2 weight %; The content of said toughner is 3-10 weight %, and the content of said ester exchange inhibitor is 0.2-2 weight %, and the said content that is selected from one or more materials in inhibitor, coupling agent and the photostabilizer is 0.1-5 weight %.
6. the said preparation methods that contains polyester of claim 1; It is characterized in that; This method comprises that polyester, filler, number-average molecular weight are that Vestolen PP 7052, nucleator, toughner and the ester exchange inhibitor of 2000-15000 mixed the mixture that obtains is mixing under the molten state of polyester; And with the products therefrom extruding pelletization, said ester exchange inhibitor is selected from one or more in trisodium phosphate, triphenyl phosphite and the calcium phosphate; Said polyester is ethylene glycol terephthalate and polybutylene terephthalate; Said filler is hollow ceramic microballon and/or hollow glass microbead; And the gross weight with said mixture is a benchmark; The content of said polyethylene terephthalate is 40-60 weight %, and the content of said polybutylene terephthalate is 5-30 weight %, and the content of said filler is 5-20 weight %; Said number-average molecular weight is that the polyacrylic content of 2000-15000 is 0.5-2 weight %; The content of said nucleator is 0.2-2 weight %, and the content of said toughner is 3-10 weight %, and the content of said ester exchange inhibitor is 0.2-2 weight %.
7. method according to claim 6, wherein, said nucleator is the mixture of Sorbitol dibenzal and Sodium Benzoate, the weight ratio of Sorbitol dibenzal and Sodium Benzoate is 1.5-2.5:1; The weight ratio of said nucleator and ester exchange inhibitor is 1.5-2.5:1; Said toughner is maleic anhydride grafted polyethylene octene elastomer and/or ethylene-acrylate-SY-Monomer G; Said hollow ceramic microballon and/or hollow glass microbead particulate D
50Be the 5-15 micron.
8. method according to claim 6; Wherein, This method comprises polyester, filler, number-average molecular weight, and to be Vestolen PP 7052, nucleator, toughner and the ester exchange inhibitor of 2000-15000 mix with one or more materials in being selected from inhibitor, coupling agent and photostabilizer, and said inhibitor is selected from one or more in phenolic antioxidant, amine type inhibitor, organic sulfur type antioxidant and the phosphite type inhibitor; Said coupling agent is silane coupling agent and/or aluminate coupling agent; Said photostabilizer is selected from one or more in amine type photostabilizer, azimidobenzene, the benzophenone compounds; Gross weight with this mixture is a benchmark; It is 40-60 weight % that the consumption of each material makes the content of polyethylene terephthalate in the mixture, and the content of polybutylene terephthalate is 5-30 weight %, and the content of filler is 5-20 weight %; Number-average molecular weight is that the polyacrylic content of 2000-15000 is 0.5-2 weight %; The content of nucleator is 0.2-2 weight %, and the content of toughner is 3-10 weight %, and the content of ester exchange inhibitor is 0.2-2 weight %; The content that is selected from one or more materials in inhibitor, coupling agent and the photostabilizer is 0.1-5 weight %.
9. method according to claim 8; Wherein, Polyester, filler, number-average molecular weight are Vestolen PP 7052, nucleator, toughner and the ester exchange inhibitor of 2000-15000 and are selected from rotating speed that one or more material method of mixing in inhibitor, coupling agent and the photostabilizer are included in 800-1200 rev/min and add coupling agent and filler down and mixed 2-10 minute, and then add other component and under 1500-2000 rev/min rotating speed, mixed 5-10 minute.
10. an automobile lamp makes up the escutcheon product, and this product is made by the material that contains polyester, it is characterized in that, the said material that contains polyester is any described material among the claim 1-5.
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| CN103387710B (en) * | 2012-05-08 | 2016-08-24 | 合肥杰事杰新材料股份有限公司 | A kind of polypropylene/polyester alloy material and its preparation method and application |
| CN102850661B (en) * | 2012-07-20 | 2014-08-27 | 深圳市科聚新材料有限公司 | Halogen-free flame-retardant PP/polyester alloy and preparation method thereof |
| CN103289329B (en) * | 2013-04-12 | 2015-05-20 | 福建奥峰科技有限公司 | Flame-retardant reinforced PET/PBT/LDPE alloy material and preparation method thereof |
| CN103232686B (en) * | 2013-04-30 | 2015-03-11 | 东莞市百思特塑胶有限公司 | Enhanced flame-retardant environmentally-friendly PBT (Polybutylece Terephthalate) with high CTI (Comparative Tracking Index) and high glowing filament |
| CN104448733A (en) * | 2014-12-10 | 2015-03-25 | 惠州市昌亿科技股份有限公司 | Reinforcing toughening agent for 3D printing PBT and PBT composite material prepared from reinforcing toughening agent |
| CN104861596A (en) * | 2015-06-09 | 2015-08-26 | 北京华腾新材料股份有限公司 | High-property polyester alloy material and preparation method thereof |
| CN105017653A (en) * | 2015-08-19 | 2015-11-04 | 苏州凯欧曼新材料科技有限公司 | Impact resistant engineering plastic for electrical equipment and preparation method thereof |
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