High-density MAA/MAN copolymer foam plastic and preparation method thereof
Technical field
The present invention relates to a kind of MAA/MAN copolymer foam plastic, particularly a kind of high-density MAA/MAN copolymer foam plastic; Also relate to the preparation method of this high-density MAA/MAN copolymer foam plastic.
Background technology
The performance of rigid foam and its density relationship are close, and generally speaking, the mechanical properties such as compressive strength and modulus, shearing resistance and modulus, tensile strength and modulus, flexural strength and modulus increase with density.And in rigid foam, the most excellent with mechanical property, resistance toheat, the creep-resistant property of Polymethacrylimide (PMI) porous plastics.The density of current commercial PMI porous plastics is mostly at 110Kg/m
3below, its structure and performance are known by people.But need the density of PMI porous plastics to exceed 150Kg/m in some field
3above, its performance is also had higher requirement.
Document 1 " patent No. is the Chinese patent of ZL200610091394.1 " discloses a kind of MAA/AN copolymer foam plastic and preparation method thereof, and the recipe ingredient of this MAA/AN copolymer foam plastic presses row weight part ratio polyreaction and foaming forms:
The density of the MAN/AN blend foam plastics of preparing according to " patent No. is the Chinese patent of ZL200610091394.1 " disclosed preparation method is at 52 ± 3Kg/m
3time, its average compressive strength is that 0.8MPa, average modulus of compression are that 32MPa, average shear intensity are that 0.8MPa, average shear modulus are 27MPa; When density is 75 ± 3Kg/m
3time, its average compressive strength is that 1.7MPa, average modulus of compression are that 56MPa, average shear intensity are that 1.3MPa, average shear modulus are 45MPa.Such performance condition is enough to meet common service requirements, but at some special occasions, its performance is still slightly inadequate.
Document 2 " patent No. is 5928459 United States Patent (USP) " discloses a kind of preparation method taking methacrylic acid and methyl propionitrile as the PMI porous plastics of monomer, this invention is taking the methacrylonitrile of 40-60wt% and the methacrylic acid of 60-40wt% as principal monomer, add the 3rd monomer of 0-20wt%, add the mixed foaming agent of the methane amide of 0.5-8wt% and the unitary fatty alcohol of 3-8 carbon atom composition, the unsaturated ethylene based mixtures that adds 0.005-5wt% is linking agent, under the effect of at least one initiator, aggregates into multipolymer.Then in 200-260 DEG C of temperature range, foam, thermal treatment 2-6h at 100-130 DEG C, then at 180-220 DEG C thermal treatment 32-64h.Finally prepare and can stand 200 DEG C, the PMI porous plastics of 0.2-0.7MPa condition moulding sandwich structure composite material.
Document 3 " patent No. is the Chinese patent of CN1903899 " discloses a kind of MAA/AN copolymer foam plastic and preparation method thereof, use methacrylic acid, vinyl cyanide, Diisopropyl azodicarboxylate, linking agent, urea etc., water-bath pre-polymerization, 180-200 DEG C of free foaming, in 140-180 DEG C of warm air, carry out aftertreatment, preparation PMI porous plastics, but the porous plastics of preparing so easy flavescence after being heated becomes fragile.
Summary of the invention
In order to overcome the poor deficiency of existing FPGA forecast Control Algorithm real-time, the invention provides a kind of high-density MAA/MAN copolymer foam plastic.This high-density MAA/MAN copolymer foam plastic is formed by monomer methacrylic acid, monomer methacrylonitrile, initiator, linking agent, whipping agent, nucleator, density-controlling agent and molecular weight regulator polyreaction foaming.
The present invention also provides the above-specified high density MAA/MAN preparation method of copolymer foam plastic.Preparation method injects formula mixed solution in close die, isothermal reaction in strong cyclic water-bath, polymerization forms transparent or semitransparent foamed MAA/MAN copolymerization sheet, MAA/MAN copolymerization sheet carries out pre-treatment in strong recirculated hot air, foam in strong recirculated hot air through the pretreated MAA/MAN of foaming copolymerization sheet, obtain MAA/MAN copolymer foam plastic plate and carry out aftertreatment in strong recirculated hot air, prepare high-density MAA/MAN copolymer foam plastic.Owing to adding density-controlling agent N,N methylene bis acrylamide, can prepare high-density MAA/MAN copolymer foam plastic, make this high-density MAA/MAN copolymer foam plastic also there is low dielectric characteristics.
The technical solution adopted for the present invention to solve the technical problems: a kind of high-density MAA/MAN copolymer foam plastic, is characterized in forming in following ratio weight part component polyreaction foaming:
A preparation method for above-specified high density MAA/MAN copolymer foam plastic, is characterized in comprising the following steps:
Step 1, in following ratio weight part component batching, evenly mix, form stock liquid;
Step 2, stock liquid is poured in the mould of being made up of two dull and stereotyped unorganic glasses and natural rubber or EPT rubber packing circle, the distance between glass is between 15~30mm, and glass mold outside is by clamp;
Step 3, have the glass mold of stock liquid to put into strong circulator bath device filling to carry out polymerization, form foamable multipolymer sheet, polymerizing condition: 40~60 DEG C of water temperatures, time 48~72h;
Step 4, the foamed MAA/MAN copolymerization sheet that step 3 is obtained carry out pre-treatment in the strong recirculated hot air of 100~150 DEG C, pretreatment time is 0.5~2h, foam in 180~220 DEG C of strong recirculated hot airs through the pretreated MAA/MAN of foaming multipolymer sheet, foamed time is 30~40min, the plastic foamboard obtaining carries out aftertreatment 2~8h in 150~170 DEG C of strong recirculated hot airs, obtains high-density MAA/MAN copolymer foam plastic.
Described initiator is any of Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or 2,2'-Azobis(2,4-dimethylvaleronitrile).
Described linking agent is any of acrylamide or Methacrylamide.
Described whipping agent is the composite foamable agent of methane amide and monohydroxy-alcohol composition.
Described monohydroxy-alcohol is any of propyl alcohol, butanols, amylalcohol or hexanol.
Described nucleator is any of urea or dimethyl urea.
Described density-controlling agent is N,N methylene bis acrylamide or N, any of N-bis-amido ditane type bismaleimidess.
Described molecular weight regulator is any of n-dodecyl mercaptan or quadrol.
The invention has the beneficial effects as follows: because the preparation method of high-density MAA/MAN copolymer foam plastic is by monomer methacrylic acid, monomer methacrylonitrile, initiator, linking agent, whipping agent, nucleator, density-controlling agent and molecular weight regulator mixed solution inject in close die, isothermal reaction in strong cyclic water-bath, polymerization forms transparent or semitransparent foamed MAA/MAN copolymerization sheet, MAA/MAN copolymerization sheet carries out pre-treatment in strong recirculated hot air, foam in strong recirculated hot air through the pretreated MAA/MAN of foaming copolymerization sheet, obtain MAA/MAN copolymer foam plastic plate and carry out aftertreatment in strong recirculated hot air, prepare high-density MAA/MAN copolymer foam plastic.Owing to adding density-controlling agent N,N methylene bis acrylamide, the density of the MAA/MAN copolymer foam plastic of preparing is by 110~150Kg/m of background technology
3bring up to 200~450Kg/m
3, and there is low dielectric characteristics.
Below in conjunction with drawings and Examples, the present invention is elaborated.
Brief description of the drawings
Fig. 1 is the preparation method's of high-density MAA/MAN copolymer foam plastic of the present invention schema.
Embodiment
Describe the present invention in detail with reference to Fig. 1.
A kind of high-density MAA/MAN copolymer foam plastic provided by the invention, by following component by weight hybrid reaction obtain:
Monomer: methacrylic acid (MAA), its weight ratio part is 42~52;
Monomer: methacrylonitrile (MAN), its weight ratio part is 58~48;
Initiator: adopt Diisopropyl azodicarboxylate (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN) or 2,2'-Azobis(2,4-dimethylvaleronitrile) (AMBN), its weight ratio part is 0.04~2.0;
Linking agent: adopt acrylamide (AM), Methacrylamide (MAM), its weight ratio part is 1.0~4.0;
Whipping agent: adopt the composite foamable agent of methane amide, monohydroxy-alcohol or both compositions, unary alcohol whipping agent comprises propyl alcohol, butanols, amylalcohol or hexanol, and weight ratio part of whipping agent is 0.1~8.0;
Nucleator: adopt urea, dimethyl urea, its weight ratio part is 0.3~1.5;
Density-controlling agent: adopt N,N methylene bis acrylamide (MBA), N, N-bis-amido ditane type bismaleimidess (BMI), its weight ratio part is 0.01~0.5;
Molecular weight regulator: adopt n-dodecyl mercaptan, quadrol, its weight ratio part is 0.01~0.1.
Embodiment 1: recipe ingredient is pressed row weight part ratio composition: 42 parts of methacrylic acids, 58 parts of methacrylonitriles, 0.6 part of Diisopropyl azodicarboxylate, 1.0 parts of acrylamides, 4.0 parts of methane amides, 1.0 parts of urea, 0.02 part of N,N methylene bis acrylamide, 0.1 part of n-dodecyl mercaptan.According to recipe ingredient configuration stock liquid, stock liquid is poured in the mould of being made up of two dull and stereotyped unorganic glasses and rubber seal, the distance between glass is 20mm, glass mold outside is by clamp; There is the glass mold of stock liquid to put into strong circulator bath device filling and carry out polymerization, polymerizing condition: 48 DEG C of water temperatures, reaction 48~72h.The foamed MAA/MAN multipolymer sheet that upper step is obtained (as baking oven, drying tunnel etc.) in the strong recirculated hot air of 120 DEG C carries out pre-treatment, pretreatment time is 1h, foam through the pretreated MAA/MAN of foaming multipolymer sheet (as baking oven, drying tunnel etc.) in 210 DEG C of strong recirculated hot airs, foamed time is 30~40min, the plastic foamboard obtaining (as baking oven, drying tunnel etc.) in 160 DEG C of strong recirculated hot airs carries out aftertreatment 2h, prepare the cystose that thickness is 30~40mm, the density of cystose is 150~200kg/m
3.
Embodiment 2: recipe ingredient is pressed row weight part ratio composition: 42 parts of methacrylic acids, 58 parts of methacrylonitriles, 0.7 part of Diisopropyl azodicarboxylate, 2.0 parts of acrylamides, 4.0 parts of methane amides, 1.0 parts of urea, 0.05 part of N,N methylene bis acrylamide, 0.1 part of n-dodecyl mercaptan.According to recipe ingredient configuration stock liquid, stock liquid is poured in the mould of being made up of two dull and stereotyped unorganic glasses and rubber seal, the distance between two dull and stereotyped unorganic glasses is 20mm.Polymerizing condition is in this case: 46 DEG C of water temperatures, reaction 48~72h.The foamed MAA/MAN multipolymer sheet that upper step is obtained (as baking oven, drying tunnel etc.) in the strong recirculated hot air of 140 DEG C carries out pre-treatment, pretreatment time is 1h, foam through the pretreated MAA/MAN of foaming multipolymer sheet (as baking oven, drying tunnel etc.) in 210 DEG C of strong recirculated hot airs, foamed time is 30~40min, the plastic foamboard obtaining (as baking oven, drying tunnel etc.) in 160 DEG C of strong recirculated hot airs carries out aftertreatment 3h, the thickness of the cystose making is 30~40mm, and density is 150~250kg/m
3.
Embodiment 3: recipe ingredient is pressed row weight part ratio composition: 42 parts of methacrylic acids, 58 parts of methacrylonitriles, 0.6 part of Diisopropyl azodicarboxylate, 2.5 parts of acrylamides, 3.0 parts of methane amides, 1.0 parts of urea, 0.1 part of N,N methylene bis acrylamide, 0.1 part of n-dodecyl mercaptan.According to recipe ingredient configuration stock liquid, stock liquid is poured in the mould of being made up of two dull and stereotyped unorganic glasses and rubber seal, the distance between glass is 20mm, glass mold outside is by clamp; Having the glass mold of stock liquid to put into strong circulator bath device filling carries out polymerization and forms the multipolymer sheet of hard, clear, polymerizing condition: 49 DEG C of water temperatures, the time is 48~72h.The foamed MAA/MAN multipolymer sheet that upper step is obtained (as baking oven, drying tunnel etc.) in the strong recirculated hot air of 140 DEG C carries out pre-treatment, pretreatment time is 1h, foam through the pretreated MAA/MAN of foaming multipolymer sheet (as baking oven, drying tunnel etc.) in 200 DEG C of strong recirculated hot airs, foamed time is 30~40min, the plastic foamboard obtaining (as baking oven, drying tunnel etc.) in 160 DEG C of strong recirculated hot airs carries out aftertreatment 4h, prepare the cystose that thickness is 25~35mm, the density of cystose is 200~300kg/m
3.
Embodiment 4: recipe ingredient is pressed row weight part ratio composition: 42 parts of methacrylic acids, 58 parts of methacrylonitriles, 0.6 part of Diisopropyl azodicarboxylate, 3.5 parts of acrylamides, 1.0 parts of methane amides, 0.5 part of urea, 0.2 part of N,N methylene bis acrylamide, 0.1 part of n-dodecyl mercaptan.According to recipe ingredient configuration stock liquid, stock liquid is poured in the mould of being made up of two dull and stereotyped unorganic glasses and rubber seal, the distance between glass is 20mm, glass mold outside is by clamp; Having the glass mold of stock liquid to put into strong circulator bath device filling carries out polymerization and forms the multipolymer sheet of hard, clear, polymerizing condition: 48 DEG C of water temperatures, reaction 48~72h.The foamed MAA/MAN multipolymer sheet that upper step is obtained (as baking oven, drying tunnel etc.) in the strong recirculated hot air of 140 DEG C carries out pre-treatment, pretreatment time is 1h, foam through the pretreated MAA/MAN of foaming multipolymer sheet (as baking oven, drying tunnel etc.) in 200 DEG C of strong recirculated hot airs, foamed time is 30~40min, the plastic foamboard obtaining (as baking oven, drying tunnel etc.) in 160 DEG C of strong recirculated hot airs carries out aftertreatment 5h, prepare the cystose that thickness is 25~30mm, the density of cystose is 250~350kg/m
3.
Embodiment 5: recipe ingredient is pressed row weight part ratio composition: 42 parts of methacrylic acids, 58 parts of methacrylonitriles, 0.5 part of Diisopropyl azodicarboxylate, 4.0 parts of acrylamides, 1.0 parts of methane amides, 0.5 part of urea, 0.3 part of N,N methylene bis acrylamide, 0.1 part of n-dodecyl mercaptan.According to recipe ingredient configuration stock liquid, stock liquid is poured in the mould of being made up of two dull and stereotyped unorganic glasses and rubber seal, the distance between glass is 20mm, glass mold outside is by clamp; Having the glass mold of stock liquid to put into strong circulator bath device filling carries out polymerization and forms the multipolymer sheet of hard, clear, polymerizing condition: 49 DEG C of water temperatures, reaction 48~72h.The foamed MAA/MAN multipolymer sheet that upper step is obtained (as baking oven, drying tunnel etc.) in the strong recirculated hot air of 140 DEG C carries out pre-treatment, pretreatment time is 1h, foam through the pretreated MAA/MAN of foaming multipolymer sheet (as baking oven, drying tunnel etc.) in 195 DEG C of strong recirculated hot airs, foamed time is 30~40min, the plastic foamboard obtaining (as baking oven, drying tunnel etc.) in 160 DEG C of strong recirculated hot airs carries out aftertreatment 5h, prepare the cystose that thickness is 25~30mm, the density of cystose is 300~450kg/m
3.
The Main Mechanical of high-density MAA/MAN copolymer foam plastic is as shown in table 1, and the high-frequency dielectric performance of its 10GHz is as shown in table 2.
The salient features of table 1 high-density MAA/MAN copolymer foam plastic
The high-frequency dielectric performance of table 2 high-density MAA/MAN copolymer foam plastic 10GHz