CN108164959A - Halogen-free flameproof polypropylene carbonate foamed material and preparation method and application - Google Patents
Halogen-free flameproof polypropylene carbonate foamed material and preparation method and application Download PDFInfo
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- CN108164959A CN108164959A CN201711445085.4A CN201711445085A CN108164959A CN 108164959 A CN108164959 A CN 108164959A CN 201711445085 A CN201711445085 A CN 201711445085A CN 108164959 A CN108164959 A CN 108164959A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/125—Water, e.g. hydrated salts
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0038—Use of organic additives containing phosphorus
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/10—Water or water-releasing compounds
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- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
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- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
Abstract
The invention discloses a kind of halogen-free flameproof polypropylene carbonate foamed materials and preparation method and application, belong to environmentally friendly foam technology field.It is difficult to have both cushion performance, flame retardant property and environmental-friendly performance to solve the problems, such as existing amortizing packaging material.The foamed material of the present invention, including：100 parts by weight polypropylene carbonates, the starch of 10 200 parts by weight and/converted starch, the foaming agent of 1 16 parts by weight, the foaming nucleation agent of 0.5 5 parts by weight, the fire-retardant compound of 10 60 parts by weight, 0 10 parts by weight fire retarding synergists, the degradable toughened resin of 0 100 parts by weight.The foamed material is obtained via expressed water foaming technique, and expansion ratio is halogen-free, Environmental Safety up to 30 times, limit oxygen index is up to 35%, 94 flame retardant ratings of UL have excellent flame retardant property and cushion performance, are suitable as packaging material application up to 0 grade of V.
Description
Technical field
The invention belongs to environmentally friendly foam technology fields, and in particular to a kind of halogen-free flameproof polypropylene carbonate foam material
Material and preparation method and application.
Background technology
In recent years, with the promotion of environmental consciousness, the use of halogen-free flameproof foamed material has been to be concerned by more and more people
And attention, as the industry size of the products such as economic fast development, all kinds of electronic apparatus goes from strength to strength, the sales volume of the product is violent
Increase, required bubble wrap material etc. increases rapidly therewith, and the use of wherein a big chunk bubble wrap material needs to have
Flame retardant property.Thus, the degradation characteristic and flame-retardancy requirements to bubble wrap material are also higher and higher, this just needs bubble wrap material
Material both has excellent cushion performance, also to have both environmental protection characteristic, with greater need for having certain flame retardant property.
Polypropylene carbonate (PPC, also known as poly (propylene carbonate) or lined polymethyl ethylene carbonate) is a kind of polymeric fatty
Adoption ester is carbon dioxide-epoxy propane copolymer, is one of now generally acknowledged degradable green plastic product, is had certain
Rigidity and intensity, close to the mechanical performance of common plastics, degradation needs under given conditions, and it is common it is daily under the conditions of
The performance of some time can be kept not change, be applied to buffering package easily-consumed products field, present buffering package rubbish can be solved
The increased problem of environmental pollution of rubbish.But since PPC belongs to amorphous polymer, and Chain Flexibility is big, intermolecular interaction
Power is small, makes that its glass transition temperature is low and mechanical property is poor, thus limits its application field.Therefore, a large amount of scholar
PPC is carried out and has been modified work, further to expand its application range.
The domestic research that PPC materials are applied to foamed material field is fewer at present, more rarely has research to have anti-flammability
The PPC bubble wrap materials of matter, wherein the Dong Lisong researcher seminar of Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences is in water
The doctoral thesis of many work, wherein doctor Wang Shusheng has been done in terms of foaming technique《Polymeric foamed material Water blown prepares skill
Art and basic research》In describe in detail PPC materials Water blown technology of preparing, the density of gained PPC foams can be
0.031-0.872g/cm3Between regulate and control, i.e., highest expansion ratio can reach the hair of 40 times and expandable polystyrene (EPS)
It is close to steep multiplying power, but does not mention the flame-retardant nature of the material in text.In its corresponding patent (application number CN201210284926)
Specify the particular technique of PPC Water blowns, content is not directed to the flame-retardant nature of foam.Chinese Academy of Sciences's Changchun applied chemistry study
Many work, patent (application number has also been made in the foaming work of PPC materials in Suo Wangxianhong researcher seminar
201310675554.7) chemical blowing of PPC materials is referred in, does not refer to the flame-retardant modified of PPC foamed materials.South China science and engineering
The Master degree candidate of university Peng Xiangfang professors is in its Master's thesis《The preparation of polypropylene carbonate composite material and its foam performance
Research》In refer to the foam characteristics of PPC materials, wherein what is mainly studied is supercritical carbon dioxide to PPC composite bodies
The foam performance research of system, wherein not mentioning the anti-flammability of PPC materials, seminar should to PPC materials in the Meng Yue of Zhongshan University
Many work is done for bubble wrap material, doctoral candidate Guan Litao is in its paper《Lined polymethyl ethylene carbonate
Chemical blowing and processing modified》And described in detail in the patent of Publication No. CN1670086A PPC materials chemical blowing and
It is processing modified, but wherein it is not directed to the flame-retardant modified of foamed material.
Invention content
The technical problem to be solved in the present invention is that existing amortizing packaging material is difficult to have both cushion performance, flame retardant property
The problem of with environmental-friendly performance, provides a kind of halogen-free flameproof polypropylene carbonate foamed material and preparation method and application.
In order to solve the above-mentioned technical problem, the present invention proposes following technical solution：
Halogen-free flameproof polypropylene carbonate foamed material, including：
The fire-retardant compound is (0.2-0.8) by mass ratio:Component A and the B component composition of (0.8-0.2), the A groups
Be divided into it is one or more in aluminium hydroxide, magnesium hydroxide, hydrotalcite, the B component for cladding ammonium polyphosphate, cladding it is red
It is one or more in phosphorus, melamine, tripolyphosphate cyanurate, melamine phosphate, ammonium dihydrogen phosphate；
The fire retarding synergist is zinc borate, one or two kinds of in expansible graphite, boric acid, molybdenum oxide.
Preferably, the starch is cornstarch, wheaten starch, potato starch, tapioca, green starch, wax
The mixture of one or more of cornstarch, sweet potato starch.
Preferably, the converted starch is pre-gelatinized starch, acidified starch, oxidized starch, etherification starch, esterification starch
One or more of mixture, the starch in converted starch is cornstarch, wheaten starch, potato starch, tapioca,
One kind in green starch, waxy corn starch, sweet potato starch.
Preferably, the foaming agent is water.
Preferably, the foaming nucleation agent for calcium carbonate, talcum powder, boron nitride, silica, zinc oxide, calcium oxide,
In magnesia, kaolin, diatomite, citric acid, mica, sodium chloride, magnesium sulfate, sodium benzoate, alundum (Al2O3), titanium dioxide
One or more of mixtures.
Preferably, the degradable toughened resin is copolymerized fourth diester, polymerized thylene carbonate third for polyadipate terephthalic acid (TPA)
The mixing of one or more of ester polyurethane elastomer, polyhydroxyalkanoate, polycaprolactone, poly butylene succinate
Object.
Preparation method the present invention also provides above-mentioned halogen-free flameproof polypropylene carbonate foamed material is：It, will be poly- by proportioning
Trimethylene carbonic ester, starch and/converted starch, foaming agent, foaming nucleation agent, fire-retardant compound, fire retarding synergist and degradable increasing
Tough resin agitating is uniformly mixed, and adds in continuous extrusion equipment, and extrusion foaming obtains expanded material.
Preferably, the mixing time is 1-8min, and rotating speed 500-2000 turns/min.
Preferably, the continuous extrusion equipment is single screw extrusion machine or double screw extruder, and the continuous extrusion is set
Standby draw ratio is more than 30.
The present invention also provides application of the above-mentioned halogen-free flameproof polypropylene carbonate foamed material as packaging material.
Compared with prior art, beneficial effects of the present invention：
1st, halogen-free flameproof polypropylene carbonate foamed material prepared by the present invention, up to 30 times, limit oxygen refers to expansion ratio
Number, up to V-0 grades, has excellent flame retardant property, cushion performance and environmental-protecting performance, is suitable as buffering up to 35%, UL94
Packaging material application.
2nd, the preparation method of halogen-free flameproof polypropylene carbonate foamed material prepared by the present invention is not used and contains halogen
Fire-retardant compound, it is environmentally friendly, and be emphasized that through specific fire-retardant compound compounded technology so that it is fire-retardant
The addition of compound in the presence of foaming agent water, does not reduce expansion ratio, and expansion ratio ensure that whole up to more than 30
The foamed state of a mixture system so that final foamed material can keep lighting, and cushion performance is maintained.
3rd, the preparation method of halogen-free flameproof polypropylene carbonate foamed material prepared by the present invention carries out PPC and starch
Blending, starch is not only as the carrier of foaming agent, but also forms the carbon forming agent in flame-retardant system, and the addition of starch can be in certain journey
The glass transition temperature of PPC is improved on degree, while by PPC/ starch materials prepared by water secondary process with more outstanding
Cushion performance, the application of PPC will be extended, and both ensure the promotion of performance, while the reduction of price.
4th, the preparation method of halogen-free flameproof polypropylene carbonate foamed material prepared by the present invention is foaming agent using water,
Technology production process is simple and environmentally-friendly, safety, operability are strong.
Specific embodiment
In order to further appreciate that the present invention, the preferred embodiments of the invention are retouched With reference to embodiment
It states, but it is to be understood that the spy that these descriptions are intended merely to further illustrate the present invention weighs just with advantage rather than to the present invention
The limitation of profit requirement.
The present invention provides a kind of halogen-free flameproof polypropylene carbonate foamed material, including：The poly- trimethylene carbonic acid of 100 parts by weight
Ester, the starch of 10-200 parts by weight and/converted starch, the foaming agent of 1-16 parts by weight, 0.5-5 parts by weight foaming nucleation agent,
Fire-retardant compound, 0-10 parts by weight fire retarding synergist, the degradable toughened resin of 0-100 parts by weight of 10-60 parts by weight.The foaming
Multiplying power is 12-35 multiplying powers, and limit oxygen index (LOI) reaches V-0 grades for 25-35%, UL94.
Wherein, starch for cornstarch, wheaten starch, potato starch, tapioca, green starch, waxy corn starch,
The mixture of one or more of sweet potato starch.Converted starch is pre-gelatinized starch, acidified starch, oxidized starch, is etherified and forms sediment
The mixture of one or more of powder, esterification starch, the starch in converted starch is cornstarch, wheaten starch, potato form sediment
One kind in powder, tapioca, green starch, waxy corn starch, sweet potato starch.In the present invention, starch is both as foaming
The carrier of agent, and the carbon forming agent in flame-retardant system is formed, and the addition of starch can improve the vitrifying of PPC to a certain extent
Transition temperature, while there is more outstanding slow performance by PPC/ starch materials prepared by water secondary process, the application of PPC will
It is extended, has both ensured the promotion of performance, while the reduction of price.Starch and/converted starch are preferably 30-180 weight
Part, more preferably 70-120 parts by weight.
Foaming agent is water.Foaming agent is preferably 6-13 parts by weight, more preferably 8-12 parts by weight.
Foaming nucleation agent is calcium carbonate, talcum powder, boron nitride, silica, zinc oxide, calcium oxide, magnesia, kaolinite
One kind or several in soil, diatomite, citric acid, mica, sodium chloride, magnesium sulfate, sodium benzoate, alundum (Al2O3), titanium dioxide
The mixture of kind.Foaming nucleation agent is preferably 1-4 parts by weight, more preferably 2-4 parts by weight.
Fire-retardant compound is (0.2-0.8) by mass ratio:Component A and the B component composition of (0.8-0.2), component A is hydrogen-oxygen
Change one or more, preferably two or three of the mixing in aluminium, magnesium hydroxide, hydrotalcite, B component is cladding polyphosphoric acids
Ammonium, encapsulated red phosphorus, melamine, tripolyphosphate cyanurate, melamine phosphate, one kind in ammonium dihydrogen phosphate or more
Kind.Fire-retardant compound is preferably 20-50 parts by weight.It should be noted that composition and proportioning that fire-retardant compound uses must be
In the range of the limitation, if beyond the range or replacing with other fire-retardant compounds, in the presence of foaming agent water, it can reduce
The expansion ratio of foamed material can not realize its cushion performance.
Fire retarding synergist is the mixture of one or more of zinc borate, expansible graphite, boric acid, molybdenum oxide.It is fire-retardant
The fire-retardant compound of synergist is preferably 2-8 parts by weight, more preferably 4-6 parts by weight.
The degradable preferred polyadipate terephthalic acid (TPA) copolymerization fourth diester (PBAT) of toughened resin, the poly- ammonia of poly (propylene carbonate)
Ester elastomer (PPC-TPU), polyhydroxyalkanoate (PHAs), polycaprolactone (PCL), in poly butylene succinate (PBS)
One or more of mixtures.Degradable toughened resin is preferably 10-80 parts by weight, more preferably 20-80 parts by weight.
The preparation method of the halogen-free flameproof polypropylene carbonate foamed material of the present invention, poly- trimethylene carbonic acid is taken according to formula
Ester, starch and/converted starch, foaming agent, foaming nucleation agent, fire-retardant compound, fire retarding synergist and degradable toughened resin, first
It adds in homogenizer and is uniformly mixed, then add in continuous extrusion equipment, expanded material is made in extrusion foaming.
Wherein, the high-speed stirred time is 1-8min, and rotating speed 500-2000 turns/min.Continuous extrusion equipment can be single screw rod
Extruder or double screw extruder；In order to which the mixture is made to be plasticized in screw rod fully, used screw slenderness ratio is excellent
Choosing is more than 30.Extrusion temperature is preferably 80-175 DEG C.
The halogen-free flameproof polypropylene carbonate foamed material of the present invention can be used as packaging material, be particularly suitable for making
For logistics amortizing packaging material.
It further illustrates the present invention with reference to embodiments.Each substance enumerated in the present embodiment is commercially available, is easily obtained
It takes.
Embodiment 1
Halogen-free flameproof polypropylene carbonate foamed material is formed sediment by the corn of 100 parts by weight polypropylene carbonates, 10 parts by weight
Powder, the foaming agent water of 3 parts by weight, the foaming nucleation agent talcum powder of 0.5 parts by weight, 10 parts by weight fire-retardant compound (wherein hydrogen
2 parts by weight of magnesia, 3 parts by weight of aluminium hydroxide, 3 parts by weight of cladding ammonium polyphosphate, 2 parts by weight of tripolyphosphate cyanurate)
It is formed with 5 parts by weight fire retarding synergists (wherein 2 parts by weight of zinc borate, 3 parts by weight of expansible graphite).
The preparation method of above-mentioned halogen-free flameproof polypropylene carbonate foamed material, first weighs each component by proportioning, then will
Cornstarch, polypropylene carbonate, foaming nucleation agent, fire-retardant compound and fire retarding synergist are added to homogenizer high speed
2min is stirred, is subsequently added into foaming agent, continues high-speed stirred 3min, mixing speed is always 1200 turns/min, finally will blending
Material afterwards is added in double screw extruder, directly carries out extrusion foaming, obtains halogen-free flameproof polypropylene carbonate foam material
Material.
Extrusion foaming system parameter setting：
Temperature setting is followed successively by 80 DEG C, 90 DEG C, 140 DEG C, 160 DEG C, 175 DEG C, 175 DEG C, 170 DEG C, machine since the spout
150 DEG C of mouth mold of head；
Extruder screw rotating speed, 150 turns/min, feeding rotating speed, 15 turns/min, screw slenderness ratio 40.
Obtained foamed material is detected, result is：Expansion ratio is 6, limit oxygen index (LOI) is 26.5%,
UL94 is V-1 grades.
Embodiment 2
Halogen-free flameproof polypropylene carbonate foamed material, by 100 parts by weight polypropylene carbonates, 30 parts by weight PPC-TPU,
The wheaten starch of 20 parts by weight, 30 parts by weight Corn starch, the foaming agent water of 5 parts by weight, 2 parts by weight foaming nucleation agent carbonic acid
Fire-retardant compound (wherein 5 parts by weight of magnesium hydroxide, 5 parts by weight of aluminium hydroxide, cladding 8 weight of ammonium polyphosphate of calcium, 20 parts by weight
Measure part, 2 parts by weight of tripolyphosphate cyanurate) and 6 parts by weight fire retarding synergists (wherein 3 parts by weight of zinc borate, expansible graphite
3 parts by weight) composition.
The preparation method of above-mentioned halogen-free flameproof polypropylene carbonate foamed material, first weighs each component by proportioning, then will
Wheaten starch, cornstarch, polypropylene carbonate, PPC-TPU, foaming nucleation agent, fire-retardant compound and fire retarding synergist add in
2min is stirred to homogenizer high speed, is subsequently added into foaming agent, continues high-speed stirred 5min, mixing speed is 500 always
Turn/min, finally the material after blending is added in double screw extruder, directly carries out extrusion foaming, halogen-free flameproof is obtained and gathers
Trimethylene carbonic ester foamed material.
Extrusion foaming system parameter setting：
Temperature setting is followed successively by 80 DEG C, 90 DEG C, 140 DEG C, 160 DEG C, 175 DEG C, 175 DEG C, 170 DEG C, machine since the spout
150 DEG C of mouth mold of head；
Extruder screw rotating speed, 200 turns/min, feeding rotating speed, 20 turns/min, screw slenderness ratio 40.
Obtained foamed material is detected, result is：Expansion ratio 8, limit oxygen index (LOI) are 28%, UL94
It is V-1 grades.
Embodiment 3
Halogen-free flameproof polypropylene carbonate foamed material, by 100 parts by weight polypropylene carbonates, the para arrowroot of 80 parts by weight
Powder, the foaming agent water of 10 parts by weight, the foaming nucleation agent talcum powder of 3 parts by weight, 40 parts by weight fire-retardant compound (wherein hydrogen-oxygen
Change magnesium 15 parts by weight, 15 parts by weight of hydrotalcite, 10 parts by weight of cladding ammonium polyphosphate), 5 parts by weight fire retarding synergist (wherein boron
Sour 2 parts by weight of zinc, 3 parts by weight of expansible graphite) and the degradable toughened resin of 50 parts by weight (wherein 10 parts by weight of polycaprolactone,
40 parts by weight of polyadipate terephthalic acid (TPA) copolymerization fourth diester) composition.
The preparation method of above-mentioned halogen-free flameproof polypropylene carbonate foamed material, first weighs each component by proportioning, then will
Tapioca, polypropylene carbonate, foaming nucleation agent and degradable toughened resin are added to the stirring of homogenizer high speed
2min is subsequently added into foaming agent, fire-retardant compound and fire retarding synergist and continues high-speed stirred 3min, and mixing speed is 1200 always
Turn/min, finally the material after blending is added in double screw extruder, directly carries out extrusion foaming, halogen-free flameproof is obtained and gathers
Trimethylene carbonic ester foamed material.
Extrusion foaming system parameter setting：
Temperature setting be followed successively by since the spout 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C, 190 DEG C, 175 DEG C, 170 DEG C,
170 DEG C of machine head port mould；
Extruder screw rotating speed, 150 turns/min, feeding rotating speed, 15 turns/min, screw slenderness ratio 40.
Obtained foamed material is detected, result is：Expansion ratio 12, limit oxygen index (LOI) are 26%, UL94
It is V-0 grades.
Embodiment 4
Halogen-free flameproof polypropylene carbonate foamed material, the wax by 100 parts by weight polypropylene carbonates, 50 parts by weight are beautiful
Rice starch, the foaming agent water of 5 parts by weight, the foaming nucleation agent talcum powder of 2 parts by weight, 20 parts by weight fire-retardant compound (wherein
2 parts by weight of hydrotalcite, 2 parts by weight of aluminium hydroxide, 16 parts by weight of tripolyphosphate cyanurate) and 5 parts by weight fire retarding synergist (its
Middle 2 parts by weight of zinc borate, 3 parts by weight of expansible graphite) composition.
The preparation method of above-mentioned halogen-free flameproof polypropylene carbonate foamed material, first weighs each component by proportioning, then will
Waxy corn starch, polypropylene carbonate, foaming nucleation agent, fire-retardant compound and fire retarding synergist are added in homogenizer
High-speed stirred 2min is subsequently added into foaming agent, continues high-speed stirred 3min, and mixing speed is always 1200 turns/min, finally will
Material after blending is added in double screw extruder, directly carries out extrusion foaming, obtains halogen-free flameproof polypropylene carbonate bubble
Foam material.
Extrusion foaming system parameter setting：
Temperature setting is followed successively by 70 DEG C, 100 DEG C, 140 DEG C, 160 DEG C, 175 DEG C, 175 DEG C, 170 DEG C, machine since the spout
140 DEG C of mouth mold of head；
Extruder screw rotating speed, 200 turns/min, feeding rotating speed, 15 turns/min.
Obtained foamed material is detected, result is：Expansion ratio 15, limit oxygen index (LOI) are 27%, UL94
It is V-1 grades.
Embodiment 5
Halogen-free flameproof polypropylene carbonate foamed material, the wax by 100 parts by weight polypropylene carbonates, 50 parts by weight are beautiful
Rice starch, the foaming agent water of 5 parts by weight, the foaming nucleation agent talcum powder of 2 parts by weight, 20 parts by weight fire-retardant compound (wherein
2 parts by weight of hydrotalcite, 2 parts by weight of aluminium hydroxide, 16 parts by weight of tripolyphosphate cyanurate) and 5 parts by weight fire retarding synergist (its
Middle 2 parts by weight of zinc borate, 3 parts by weight of expansible graphite) composition.
The preparation method of above-mentioned halogen-free flameproof polypropylene carbonate foamed material, first weighs each component by proportioning, then will
Waxy corn starch, polypropylene carbonate, foaming nucleation agent, fire-retardant compound and fire retarding synergist are added in homogenizer
High-speed stirred 2min is subsequently added into foaming agent, continues high-speed stirred 3min, and mixing speed is always 1200 turns/min, finally will
Material after blending is added in double screw extruder, directly carries out extrusion foaming, obtains halogen-free flameproof polypropylene carbonate bubble
Foam material.
Extrusion foaming system parameter setting：
Temperature setting is followed successively by 70 DEG C, 100 DEG C, 140 DEG C, 160 DEG C, 175 DEG C, 175 DEG C, 170 DEG C, machine since the spout
140 DEG C of mouth mold of head；
Extruder screw rotating speed, 200 turns/min, feeding rotating speed, 15 turns/min.
Obtained foamed material is detected, result is：Expansion ratio 16, limit oxygen index (LOI) are 29%, UL94
It is V-0 grades.
Embodiment 6
Halogen-free flameproof polypropylene carbonate foamed material, by 100 parts by weight polypropylene carbonates, the corn of 100 parts by weight
Starch, 50 parts by weight pre-gelatinized starches, the foaming agent water of 10 parts by weight, the foaming nucleation agent talcum powder of 1 parts by weight, 25 parts by weight
Fire-retardant compound (wherein 10 parts by weight of magnesium hydroxide, 10 parts by weight of aluminium hydroxide, cladding ammonium polyphosphate 3 parts by weight, trimerization
2 parts by weight of phosphoric acid cyanurate) and 10 parts by weight fire retarding synergists (wherein 5 parts by weight of zinc borate, 5 parts by weight of expansible graphite)
(wherein 15 parts by weight of poly (propylene carbonate) polyurethane elastomer, polyadipate are to benzene two with the degradable toughened resin of 30 parts by weight
15 parts by weight of formic acid copolymerization fourth diester) composition.
The preparation method of above-mentioned halogen-free flameproof polypropylene carbonate foamed material, first weighs each component by proportioning, then will
Cornstarch, pre-gelatinized starch, polypropylene carbonate, foaming nucleation agent and degradable toughened resin are added in homogenizer
High-speed stirred 2min is subsequently added into foaming agent, fire-retardant compound and fire retarding synergist and continues high-speed stirred 3min, mixing speed one
It is directly 800 turns/min, finally the material after blending is added in single screw extrusion machine, extrusion foaming is directly carried out, obtains nothing
Halogen flame-retardant polypropylene supports carbonic ester foamed material.
Extrusion foaming system parameter setting：
Temperature setting is followed successively by 60 DEG C, 110 DEG C, 160 DEG C, 175 DEG C, 175 DEG C, 160 DEG C, machine head port mould since the spout
145℃；
Extruder screw rotating speed, 180 turns/min, feeding rotating speed, 20 turns/min, screw slenderness ratio 40.
Obtained foamed material is detected, result is：Expansion ratio 20, limit oxygen index (LOI) are 29%, UL94
It is V-0 grades.
Embodiment 7
Halogen-free flameproof polypropylene carbonate foamed material, by 100 parts by weight polypropylene carbonates, the para arrowroot of 50 parts by weight
Powder, the cornstarch of 50 parts by weight, the foaming agent of 10 parts by weight, 5 parts by weight foaming nucleation agent talcum powder, 20 parts by weight resistance
Fire compound (wherein 8 parts by weight of magnesium hydroxide, 6 parts by weight of aluminium hydroxide, 3 parts by weight of cladding ammonium polyphosphate, ammonium dihydrogen phosphate
3 parts by weight) and the degradable toughened resin of 40 parts by weight (wherein 20 parts by weight of polycaprolactone, the copolymerization of polyadipate terephthalic acid (TPA)
20 parts by weight of fourth diester) composition.
The preparation method of above-mentioned halogen-free flameproof polypropylene carbonate foamed material, first weighs each component by proportioning, then will
Tapioca, cornstarch, polypropylene carbonate, foaming nucleation agent, fire-retardant compound and degradable toughened resin are added to height
Fast blender high speed stirs 3min, is subsequently added into foaming agent, continues high-speed stirred 3min, mixing speed always for 1000 turns/
Material after blending is finally added in double screw extruder by min, directly carries out extrusion foaming, obtains halogen-free flameproof poly- third
Support carbonic ester foamed material.
Extrusion foaming system parameter setting：
Temperature setting is followed successively by 80 DEG C, 90 DEG C, 140 DEG C, 160 DEG C, 185 DEG C, 175 DEG C, 170 DEG C, machine since the spout
150 DEG C of mouth mold of head；
Extruder screw rotating speed, 150 turns/min, feeding rotating speed, 15 turns/min, screw slenderness ratio 40.
Obtained foamed material is detected, result is：Expansion ratio 25, limit oxygen index (LOI) are 27%, UL94
It is V-1 grades.
Embodiment 8
Halogen-free flameproof polypropylene carbonate foamed material, by 100 parts by weight polypropylene carbonates, the wax of 150 parts by weight
Cornstarch, the foaming agent water of 12 parts by weight, the foaming nucleation agent talcum powder of 2 parts by weight, 40 parts by weight fire-retardant compound (its
Middle 3 parts by weight of magnesium hydroxide, 4 parts by weight of aluminium hydroxide, 3 parts by weight of hydrotalcite, 20 parts by weight of cladding ammonium polyphosphate, cladding are red
5 parts by weight of phosphorus, 5 parts by weight of tripolyphosphate cyanurate), 4 parts by weight fire retarding synergists (wherein 2 parts by weight of boric acid, inflatable stone
Black 2 parts by weight) and the degradable toughened resin of 20 parts by weight (wherein 10 parts by weight of polycaprolactone, polyadipate terephthalic acid (TPA) are total to
10 parts by weight of polybutadiene ester) composition.
The preparation method of above-mentioned halogen-free flameproof polypropylene carbonate foamed material, first weighs each component by proportioning, then will
Waxy corn starch, polypropylene carbonate, foaming nucleation agent and degradable toughened resin are added to homogenizer high speed and stir
3min is mixed, foaming agent, fire-retardant compound and fire retarding synergist is subsequently added into and continues high-speed stirred 2min, mixing speed is always
1000 turns/min, finally the material after blending is added in double screw extruder, directly carries out extrusion foaming, obtain Halogen resistance
Fire polypropylene carbonate foamed material.
Extrusion foaming system parameter setting：
Temperature setting is followed successively by 60 DEG C, 80 DEG C, 140 DEG C, 160 DEG C, 185 DEG C, 175 DEG C, 170 DEG C, machine since the spout
150 DEG C of mouth mold of head；
Extruder screw rotating speed, 150 turns/min, feeding rotating speed, 18 turns/min, screw slenderness ratio 40.
Obtained foamed material is detected, result is：Expansion ratio 30, limit oxygen index (LOI) are 28%, UL94
It is V-0 grades.
Embodiment 9
Halogen-free flameproof polypropylene carbonate foamed material, by 100 parts by weight polypropylene carbonates, the wax of 200 parts by weight
Cornstarch, the foaming agent water of 15 parts by weight, the foaming nucleation agent talcum powder of 3 parts by weight, 30 parts by weight fire-retardant compound (its
Middle 10 parts by weight of magnesium hydroxide, 10 parts by weight of aluminium hydroxide, 10 parts by weight of encapsulated red phosphorus) and 5 parts by weight fire retarding synergist (its
Middle 2 parts by weight of zinc borate, 3 parts by weight of expansible graphite).
The preparation method of above-mentioned halogen-free flameproof polypropylene carbonate foamed material, first weighs each component by proportioning, then will
Waxy corn starch, polypropylene carbonate, foaming nucleation agent, fire-retardant compound and fire retarding synergist are added in homogenizer
High-speed stirred 2min is subsequently added into foaming agent, continues high-speed stirred 3min, and mixing speed is always 1000 turns/min, finally will
Material after blending is added in single screw extrusion machine, directly carries out extrusion foaming, obtains halogen-free flameproof polypropylene carbonate bubble
Foam material.
Extrusion foaming system parameter setting：
Temperature setting is followed successively by 80 DEG C, 110 DEG C, 180 DEG C, 175 DEG C, 175 DEG C, 170 DEG C, machine head port mould since the spout
170℃；
Extruder screw rotating speed, 150 turns/min, feeding rotating speed, 18 turns/min, screw slenderness ratio 38.
Obtained foamed material is detected, result is：Expansion ratio 30, limit oxygen index (LOI) are 31%, UL94
It is V-0 grades.
Embodiment 10
Halogen-free flameproof polypropylene carbonate foamed material, by 100 parts by weight polypropylene carbonates, the corn of 100 parts by weight
Starch, 50 parts by weight pre-gelatinized starches, the foaming agent water of 12 parts by weight, the foaming nucleation agent talcum powder of 4 parts by weight, 60 parts by weight
Fire-retardant compound (wherein 20 parts by weight of magnesium hydroxide, 10 parts by weight of aluminium hydroxide, cladding ammonium polyphosphate 20 parts by weight, three
10 parts by weight of polyphosphoric acid cyanurate) and 6 parts by weight fire retarding synergists (wherein 5 parts by weight of zinc borate, 1 weight of expansible graphite
Part) and the degradable toughened resin of 30 parts by weight (wherein 15 parts by weight of poly (propylene carbonate) polyurethane elastomer, polyadipate are to benzene
15 parts by weight of dioctyl phthalate copolymerization fourth diester) composition.
The preparation method of above-mentioned halogen-free flameproof polypropylene carbonate foamed material, first weighs each component by proportioning, then will
Cornstarch, pre-gelatinized starch, polypropylene carbonate, foaming nucleation agent and degradable toughened resin are added in homogenizer
High-speed stirred 2min is subsequently added into foaming agent, fire-retardant compound and fire retarding synergist and continues high-speed stirred 3min, mixing speed one
It is directly 800 turns/min, finally the material after blending is added in single screw extrusion machine, extrusion foaming is directly carried out, obtains nothing
Halogen flame-retardant polypropylene supports carbonic ester foamed material.
Extrusion foaming system parameter setting：
Temperature setting is followed successively by 60 DEG C, 110 DEG C, 160 DEG C, 175 DEG C, 175 DEG C, 160 DEG C, machine head port mould since the spout
145℃；
Extruder screw rotating speed, 180 turns/min, feeding rotating speed, 20 turns/min, screw slenderness ratio 40.
Obtained foamed material is detected, result is：Expansion ratio 19, limit oxygen index (LOI) are 35%, UL94
It is V-0 grades.
Embodiment 11
Halogen-free flameproof polypropylene carbonate foamed material, by 100 parts by weight polypropylene carbonates, the wax of 100 parts by weight
Cornstarch, the tapioca of 50 parts by weight, the cornstarch of 50 parts by weight, the foaming agent water of 15 parts by weight, 2 parts by weight hair
Fire-retardant compound (wherein 20 parts by weight of magnesium hydroxide, 20 parts by weight of aluminium hydroxide, the packet of bubble nucleating agent talcum powder, 60 parts by weight
Cover 10 parts by weight of ammonium polyphosphate, 5 parts by weight of encapsulated red phosphorus, 5 parts by weight of tripolyphosphate cyanurate), the fire-retardant synergistic of 4 parts by weight
Agent (wherein 2 parts by weight of molybdenum oxide, 2 parts by weight of expansible graphite) and the degradable toughened resin of 100 parts by weight (wherein poly- hydroxyl fat
20 parts by weight of fat acid esters (PHAs), polyadipate terephthalic acid (TPA) copolymerization fourth diester (PBAT) 20 parts by weight, poly-succinic fourth two
60 parts by weight of alcohol ester (PBS) form.
The preparation method of above-mentioned halogen-free flameproof polypropylene carbonate foamed material, first weighs each component by proportioning, then will
Waxy corn starch, tapioca, cornstarch, polypropylene carbonate, foaming nucleation agent, fire-retardant compound, fire retarding synergist
Homogenizer high speed stirring 4min is added to degradable toughened resin, foaming agent is subsequently added into, continues high-speed stirred
4min, mixing speed are always 500 turns/min, and finally the material after blending is added in double screw extruder, is directly carried out
Extrusion foaming obtains halogen-free flameproof polypropylene carbonate foamed material.
Extrusion foaming system parameter setting：
Temperature setting is followed successively by 80 DEG C, 90 DEG C, 140 DEG C, 170 DEG C, 180 DEG C, 175 DEG C, 170 DEG C, machine since the spout
150 DEG C of mouth mold of head；
Extruder screw rotating speed, 150 turns/min, feeding rotating speed, 18 turns/min, screw slenderness ratio 38.
Obtained foamed material is detected, result is：Expansion ratio is 15, limit oxygen index (LOI) is 35%,
UL94 is V-0 grades.
Comparative example 1
Halogen-free flameproof polypropylene carbonate foamed material, by 100 parts by weight polypropylene carbonates, the wax of 100 parts by weight
Cornstarch, the tapioca of 50 parts by weight, the cornstarch of 50 parts by weight, the foaming agent water of 15 parts by weight, 2 parts by weight hair
Steep nucleating agent talcum powder, 60 parts by weight magnesium hydroxides, 4 parts by weight fire retarding synergists (wherein 2 parts by weight of molybdenum oxide, inflatable stone
Black 2 parts by weight) and the degradable toughened resin of 100 parts by weight (wherein 20 parts by weight of polyhydroxyalkanoate (PHAs), polyadipate
Terephthalic acid (TPA) copolymerization fourth diester (PBAT) 20 parts by weight, 60 parts by weight of poly butylene succinate (PBS) composition.
The preparation method of above-mentioned halogen-free flameproof polypropylene carbonate foamed material, first weighs each component by proportioning, then will
Waxy corn starch, tapioca, cornstarch, polypropylene carbonate, foaming nucleation agent, magnesium hydroxide, fire retarding synergist and
Degradable toughened resin is added to homogenizer high speed stirring 4min, is subsequently added into foaming agent, continues high-speed stirred 4min,
Mixing speed is always 500 turns/min, and finally the material after blending is added in double screw extruder, directly carries out extrusion hair
Bubble, obtains halogen-free flameproof polypropylene carbonate foamed material.
Extrusion foaming system parameter setting：
Temperature setting is followed successively by 80 DEG C, 90 DEG C, 140 DEG C, 170 DEG C, 180 DEG C, 175 DEG C, 170 DEG C, machine since the spout
150 DEG C of mouth mold of head；
Extruder screw rotating speed, 150 turns/min, feeding rotating speed, 18 turns/min, screw slenderness ratio 38.
Obtained foamed material is detected, result is：Expansion ratio is 15, limit oxygen index (LOI) is 25%,
UL94 is V-2 grades.
Comparative example 2
Halogen-free flameproof polypropylene carbonate foamed material, by 100 parts by weight polypropylene carbonates, the wax of 100 parts by weight
Cornstarch, the tapioca of 50 parts by weight, the cornstarch of 50 parts by weight, the foaming agent water of 15 parts by weight, 2 parts by weight hair
Steep nucleating agent talcum powder, the cladding ammonium polyphosphate of 60 parts by weight, 4 parts by weight fire retarding synergists (wherein 2 parts by weight of molybdenum oxide,
2 parts by weight of expansible graphite) and the degradable toughened resin of 100 parts by weight (wherein 20 parts by weight of polyhydroxyalkanoate (PHAs),
Polyadipate terephthalic acid (TPA) copolymerization fourth diester (PBAT) 20 parts by weight, 60 parts by weight of poly butylene succinate (PBS) composition.
The preparation method of above-mentioned halogen-free flameproof polypropylene carbonate foamed material, first weighs each component by proportioning, then will
Waxy corn starch, tapioca, cornstarch, polypropylene carbonate, foaming nucleation agent, cladding ammonium polyphosphate, fire-retardant association
Effect agent and degradable toughened resin are added to homogenizer high speed stirring 4min, are subsequently added into foaming agent, continue high-speed stirring
Mix 4min, mixing speed is always 500 turns/min, and finally the material after blending is added in double screw extruder, directly into
Row extrusion foaming obtains halogen-free flameproof polypropylene carbonate foamed material.
Extrusion foaming system parameter setting：
Temperature setting is followed successively by 80 DEG C, 90 DEG C, 140 DEG C, 170 DEG C, 180 DEG C, 175 DEG C, 170 DEG C, machine since the spout
150 DEG C of mouth mold of head；
Extruder screw rotating speed, 150 turns/min, feeding rotating speed, 18 turns/min, screw slenderness ratio 38.
Obtained foamed material is detected, result is：Expansion ratio is 3, limit oxygen index (LOI) is 28%,
UL94 is V-0 grades.
Obviously the explanation of above example is only intended to help to understand method and core concept of the invention.It should be pointed out that
For those skilled in the art, without departing from the principle of the present invention, can also to the present invention into
Row some improvements and modifications, these improvement and modification are also fallen within the protection scope of the claims of the present invention.
Claims (10)
1. halogen-free flameproof polypropylene carbonate foamed material, which is characterized in that including：
The fire-retardant compound is (0.2-0.8) by mass ratio:Component A and the B component composition of (0.8-0.2), the component A are
One or more in aluminium hydroxide, magnesium hydroxide, hydrotalcite, the B component is cladding ammonium polyphosphate, encapsulated red phosphorus, three
It is one or more in poly cyanamid, tripolyphosphate cyanurate, melamine phosphate, ammonium dihydrogen phosphate；
The fire retarding synergist is zinc borate, one or two kinds of in expansible graphite, boric acid, molybdenum oxide.
2. halogen-free flameproof polypropylene carbonate foamed material according to claim 1, which is characterized in that the starch is jade
One kind or several in rice starch, wheaten starch, potato starch, tapioca, green starch, waxy corn starch, sweet potato starch
The mixture of kind.
3. halogen-free flameproof polypropylene carbonate foamed material according to claim 1, which is characterized in that the converted starch
For the mixture of one or more of pre-gelatinized starch, acidified starch, oxidized starch, etherification starch, esterification starch, denaturation is formed sediment
Starch in powder is cornstarch, wheaten starch, potato starch, tapioca, green starch, waxy corn starch, sweet potato shallow lake
One kind in powder.
4. halogen-free flameproof polypropylene carbonate foamed material according to claim 1, which is characterized in that the foaming agent is
Water.
5. halogen-free flameproof polypropylene carbonate foamed material according to claim 1, which is characterized in that the foaming nucleation
Agent for calcium carbonate, talcum powder, boron nitride, silica, zinc oxide, calcium oxide, magnesia, kaolin, diatomite, citric acid,
The mixture of one or more of mica, sodium chloride, magnesium sulfate, sodium benzoate, alundum (Al2O3), titanium dioxide.
6. halogen-free flameproof polypropylene carbonate foamed material according to claim 1, which is characterized in that the degradable increasing
Tough resin for polyadipate terephthalic acid (TPA) be copolymerized fourth diester, poly (propylene carbonate) polyurethane elastomer, polyhydroxyalkanoate,
The mixture of one or more of polycaprolactone, poly butylene succinate.
7. the preparation method of the halogen-free flameproof polypropylene carbonate foamed material described in claim 1-6 any one, feature
It is, by proportioning, by polypropylene carbonate, starch and/converted starch, foaming agent, foaming nucleation agent, fire-retardant compound, fire-retardant
Synergist and degradable toughened resin are uniformly mixed, and add in continuous extrusion equipment, and extrusion foaming obtains expanded material.
8. the preparation method of halogen-free flameproof polypropylene carbonate foamed material according to claim 7, which is characterized in that institute
Mixing time is stated as 1-8min, rotating speed 500-2000 turns/min.
9. the preparation method of halogen-free flameproof polypropylene carbonate foamed material according to claim 7, which is characterized in that institute
Continuous extrusion equipment is stated as single screw extrusion machine or double screw extruder, the draw ratio of the continuous extrusion equipment is more than 30.
10. halogen-free flameproof polypropylene carbonate foamed material the answering as packaging material described in claim 1-6 any one
With.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134379A (en) * | 2011-02-24 | 2011-07-27 | 深圳市光华伟业实业有限公司 | Halogen-free antiflaming polylactic acid material and produciotn method of same |
| CN102276971A (en) * | 2011-07-21 | 2011-12-14 | 中山大学 | Fully-degradable polymethyl methacrylate ethylene carbonic ester foaming material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102134379A (en) * | 2011-02-24 | 2011-07-27 | 深圳市光华伟业实业有限公司 | Halogen-free antiflaming polylactic acid material and produciotn method of same |
| CN102276971A (en) * | 2011-07-21 | 2011-12-14 | 中山大学 | Fully-degradable polymethyl methacrylate ethylene carbonic ester foaming material and preparation method thereof |
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| CN109666271A (en) * | 2018-12-11 | 2019-04-23 | 中国科学院理化技术研究所 | A kind of fretting map degradable mulch and preparation method thereof |
| CN109666271B (en) * | 2018-12-11 | 2020-11-24 | 中国科学院理化技术研究所 | Micro-foaming degradable mulching film and preparation method thereof |
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