CN1255523A - Hot-fusible high-molecular adhesive and its preparing process - Google Patents
Hot-fusible high-molecular adhesive and its preparing process Download PDFInfo
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- CN1255523A CN1255523A CN98122120A CN98122120A CN1255523A CN 1255523 A CN1255523 A CN 1255523A CN 98122120 A CN98122120 A CN 98122120A CN 98122120 A CN98122120 A CN 98122120A CN 1255523 A CN1255523 A CN 1255523A
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Abstract
A hot-fusible high-molecular adhesive is prepared from thermoplastic plastics (especially polyolefin) as main component, initiating agent of peroxide type and polar monomer with reactive function group (2-bond) through mixing and extruding to granulate, and can be used to make high-strength plate of organic filler (wood or waste paper powder) and thermoplastic plastics (polypropylene). Its advantage is high adhesion.
Description
The invention belongs to the polymer binder field.Specifically the present invention relates to preparation hot-fusible high-molecular adhesives such as thermoplastics and peroxide initiator, polar monomers, this tackiness agent is used for the bonding between organic filler (referring to wood powder and waste paper powder especially) and the thermoplastics, and high-strength panel is extruded in preparation continuously.
The sheet material that bonding between organic filler (referring to wood powder and waste paper powder especially) and the thermoplastics (particularly polypropylene PP) is made is a kind of emerging automotive interior material, it has the excellent sound insulation heat-proof quality, cheap, easy to process, moulding is easy, is the ideal material of inside gadgets such as the panel board of making automobile, inner plate of car door, packaging tray, sun visor, top, boot.Country in many automotive industry prosperities is very general as the application of Germany and Italian this material, be at car or lorry all has application, raising along with the developing industry level of Domestic Automotive Industry, original automobile production producer that uses wood-fiber board to make panel board, car door liner, also change the organic filler/thermoplastics composite sheet that becomes to have more advantage one after another, wood powder/PP composite sheet particularly, to improve the use properties and the interior trim class of automobile, this class material requirements intensity height, good moldability, surface are easily decorated and are handled.At present, the production technology of this class material mainly contains two kinds both at home and abroad: the one, wood powder is carried out surface treatment in advance, promptly mix in high-speed mixer with wood powder with tensio-active agent such as Sodium dodecylbenzene sulfonate, coupling agent etc., it is nonpolar that the wood powder surface is become, be easy to the compound sheet material made from nonpolar PP, though this method has increased the intensity of sheet material, the composite sheet intensity of making is limited.The 2nd, the surface applying of filling wood powder/PP composite sheet is contained fused fiber shape thermoplastic plastic layer, as Chinese patent (application number: 95107766.X), this technology does not take measures to strengthen filling bonding force, material cost height and the method complex process between sawdust and/or so-called woody type material such as wood powder and/or wood wool and the polypropylene.And our desire promptly adopts the way of matrix modification from other method, matrix resin is made the hotmelt that has the polar group, add a certain amount of this type of tackiness agent, make resin easily and wood powder affine, with the bounding force between the interface of enhancing system matrix and wood powder.And about hotmelt, Chinese patent (application number: 90103064.3) disclose the method that a kind of thermoplasticity waste or used plastics is made hot melt adhesive, this invention is the particle that earlier waste and old thermoplastics is ground into below the granularity 3mm, again waste or used plastics particle and water and grinding aid (its main component is a Sodium dodecylbenzene sulfonate) are carried out the ultra-fine powder of making on the plain wheel colloidal mill, make the granularity of waste and old thermoplastics reduce to 80 microns, promptly obtain hot melt adhesive, this hot melt adhesive is used for and the mixed fabricate-heat melten gel of organic filler wood-based plate, but the described sheet material of this invention be organic filler directly with hot melt adhesive mixing mold pressing, big with the hot melt adhesive amount, and the hot melt adhesive raw material is a waste or used plastics, unstable properties, its technology is loaded down with trivial details.
The objective of the invention is at above-mentioned manufacturing process and (or) deficiency of hot melt adhesive, a kind of hotmelt that has the bonds well performance simultaneously with mineral filler and thermoplastics is provided, this hotmelt has more high-adhesive-strength, and material is even, stable performance.
The present invention also aims to provide the manufacture method of this hotmelt, this method is simple, is convenient to suitability for industrialized production.
Organic fillers such as wood powder are from particulate microscopic pattern loose, the lacunose filamentary structure of saying so, and from the physico-chemical property on surface, its specific surface area is big, and stronger adsorptivity is arranged, and the surface also has many hydroxyls, alkoxy grp.Make the thermoplastic plastic substrates melt to organic filler wetting, spreadability good, the melt of base material can penetrate in the melt-processed process in the space of organic filler and go, treat to make after the mixture cooling thermoplastic matrix tightly " embedding " in organic filler particulate space, to improve the cohesive strength of the two, and then the intensity of raising sheet material and other goods, this can be by introducing polar group in matrix, reduce the surface tension of matrix and organic filler, and improve the flowability raising organic filler particle of matrix melt and wetting realization the between the matrix.Hot-fusible high-molecular adhesive of the present invention for this reason comprises: thermoplastics (parts by weight) 100; Peroxide initiator (parts by weight) 0.1～1.5, adding the peroxide initiator is in order to make the molecular chain degradation of thermoplastics, the purpose of polar monomer in the grafting simultaneously; Polar monomer (parts by weight) 0.2～10 can make polar monomer be grafted on the thermoplastics in this scope effectively.Peroxide initiator and polar monomer purity all are not less than technical grade, contain tertiary carbon atom on the molecular chain of thermoplastics, make it be easy to degrade and can carry out grafting modification, and thermoplastics adopts polyolefine usually, as polypropylene or polyethylene.The peroxide initiator is selected from dicumyl peroxide (DCP), peroxidized t-butyl perbenzoate (TPB) or benzoyl peroxide (BPO), its parts by weight are preferably 0.3～1, polar monomer is selected unsaturated monoprotic acid or unsaturated dibasic acid or MALEIC ANHYDRIDE for use, its parts by weight are preferably 0.5～4, and unsaturated monacid structural formula is:
Wherein R is C
1～C
5Alkyl, can select vinylformic acid for use especially; The structural formula of unsaturated dibasic acid is:
R wherein
1, R
2Be respectively zero or C
1～C
3Alkyl, work as R especially
1, R
2Be respectively zero, promptly do not have R
1, R
2The time be maleic acid.
Use initiator can make the thermoplastics degraded, the polar monomer that will have reactive functional groups simultaneously is grafted on the thermoplastics molecule, further in order to prevent the excessive degradation of thermoplastics, physical strength and the resistance toheat of while in order to improve sheet material, just should make the thermoplastics that has a certain amount of higher molecular weight in the hotmelt, this crosslinking coagent that can add 0.1～5 parts by weight in prescription is again realized, crosslinking coagent purity is not less than technical grade, content is preferably 0.2～4 parts by weight, and crosslinking coagent of the present invention is preferably from three triallyl isocyanurates (TAIC), liquid polybutadiene or Vinylstyrene (DVB).
The preparation method of this hotmelt, comprise each component is mixed in high-speed mixer, need in high-speed mixer, mixing time be 2～10min generally, add in the forcing machine then, forcing machine of the present invention refers to common list, twin screw extruder, but the cocurrent and parallel twin screw extruder of good mixing effect preferably, in 160～240 ℃ of temperature ranges, squeeze granulation and make this tackiness agent, better extruder temperature scope is 180～230 ℃, and the extruder screw length-to-diameter ratio is more preferably greater than equaling 25, to guarantee that graft reaction carries out fully in extrusion.For the melt flow rate (MFR) of the mobile made hotmelt that improves the matrix melt at least greater than 10g/10min, better should be greater than 15g/10min, preferably should (load be 2.16kg greater than 30g/10min, down together), this hotmelt has good flowability, so hotmelt of the present invention and fibrous organic filler powder are (as wood powder, disregard message paper powder), has good wetting property, can be penetrated in the groove of fiber even the inside and go, again because this hotmelt has been introduced polar group in the matrix resin thermoplastics, can with the hydroxyl and the alkoxyl group generation esterification on wood powder surface, can greatly increase the adhesive capacity on wood powder and thermoplastics surface, so add the plastic plate that hotmelt of the present invention makes, have excellent physicochemical property.
Hotmelt of the present invention can be used for preparing organic filler and compound plastic plate, and this sheet material can be used for making automobile door plate, ceiling, dashboard or packing, material of construction etc.
With embodiment effect of the present invention is described below.Content is parts by weight among the embodiment 1:(embodiment) equipment and processing condition: screw diameter Φ 35mm, length-to-diameter ratio is 25: 1 a parallel double-screw extruder forcing machine.Temperature is set: 180～240 ℃, and forcing machine rotating speed: 35rpm.Prescription: polypropylene (melt flow rate (MFR) 3.2g/10min) 100
Dicumyl peroxide (DCP) 0.4
MALEIC ANHYDRIDE (MA) 1.5 embodiment 2: equipment and processing condition: with embodiment 1.Prescription: polypropylene (melt flow rate (MFR) 3.2g/10min) 100
Dicumyl peroxide (DCP) 1
MALEIC ANHYDRIDE (MA) 6
Three triallyl isocyanurates (TAIC), 1 embodiment 3: equipment and processing condition: with embodiment 1.Prescription: polypropylene (melt flow rate (MFR) 3.2g/10min) 100
Benzoyl peroxide (BPO) 0.2
MALEIC ANHYDRIDE (MA) 1.2
Vinylstyrene (DVB) 0.2 embodiment 4: equipment and processing condition: with embodiment 1.Prescription: polypropylene (melt flow rate (MFR) 3.2g/10min) 100
Benzoyl peroxide (BPO) 0.2
Vinylformic acid (AA) 1 embodiment, 5 equipment and processing condition: with embodiment 1.Prescription: polypropylene (melt flow rate (MFR) 3.5g/10min) 100
Dicumyl peroxide (DCP) 0.3
MALEIC ANHYDRIDE (MA) 1.4 embodiment, 6 equipment and processing condition: screw diameter Φ 30mm, length-to-diameter ratio is 25: 1 a single screw extrusion machine forcing machine.Temperature is set: 180～230 ℃, and forcing machine rotating speed: 30rpm.Prescription: polypropylene (melt flow rate (MFR) 3.5g/10min) 100
Dicumyl peroxide (DCP) 0.8
MALEIC ANHYDRIDE (MA) 6
Three triallyl isocyanurates (TAIC), 1 embodiment, 7 equipment and processing condition: with embodiment 6.Prescription: polypropylene (melt flow rate (MFR) 3.2g/10min) 100
Benzoyl peroxide (BPO) 0.2
MALEIC ANHYDRIDE (MA) 1.2
Vinylstyrene (DVB) 0.2 embodiment, 8 equipment and processing condition: with embodiment 6.Prescription: polypropylene (melt flow rate (MFR) 3.2g/10min) 100
Benzoyl peroxide (BPO) 0.2
Vinylformic acid (AA) 1 embodiment 9: equipment and processing condition: with embodiment 1.Prescription: polypropylene (melt flow rate (MFR) 3.2g/10min) 100
Benzoyl peroxide (BPO) 0.2
Maleic acid (MA) 1.4 embodiment 10: equipment and processing condition: with embodiment 1.Prescription: high density polyethylene(HDPE) (melt flow rate (MFR) 0.1g/10min) 100
Benzoyl peroxide (BPO) 0.2
MALEIC ANHYDRIDE (MA) 0.8 embodiment, 11 equipment and processing condition: with embodiment 6.Prescription: LLDPE (melt flow rate (MFR) 2.0g/10min) 100
Benzoyl peroxide (BPO) 0.2
The effect of MALEIC ANHYDRIDE (MA) 0.8 embodiment of the invention:
With wood powder (35 order), the hotmelt of polypropylene (melt flow rate (MFR) 3.2g/10min) and the foregoing description 1～9 was by 100: 88: 12, and with wood powder (35 order), the hotmelt of polyethylene (melt flow rate (MFR) 0.1g/10min) and the foregoing description 10～11 was by 100: 88: 12, (180～240 ℃ of extruder temperatures after mixing extrusion calendaring, 130 ℃ of rolling press temperature), the partial properties index of the plastic plate that makes is listed table 1 in, and common compound plastic plate (does not add hotmelt of the present invention, wood powder and polyacrylic ratio are 100: 100, commercially available) as Comparative Examples, its performance index are also listed table 1 in.
Table 1. effect of the present invention
| Test event | Hotmelt | Composite sheet | |||
| Melt flow rate (MFR) g/10min | Flexural strength MPa | Modulus in flexure MPa | Tensile strength MPa | Vicat softening point ℃ | |
| The employing standard | ??GB3682 | ????????GB9341 | ??GB1040 | ???GB1634 | |
| Embodiment 1 | ????21 | ????56 | ????3234 | ????32 | ????162 |
| Embodiment 2 | ????37 | ????67 | ????3800 | ????35 | ????167 |
| Embodiment 3 | ????23 | ????57 | ????3033 | ????30 | ????158 |
| Embodiment 4 | ????27 | ????49 | ????2906 | ????32 | ????158 |
| Embodiment 5 | ????23 | ????59 | ????3738 | ????32 | ????163 |
| Embodiment 6 | ????40 | ????66 | ????3790 | ????33 | ????164 |
| Embodiment 7 | ????25 | ????57 | ????3132 | ????31 | ????159 |
| Embodiment 8 | ????28 | ????51 | ????3002 | ????33 | ????159 |
| Embodiment 9 | ????25 | ????56 | ????3002 | ????29 | ????156 |
| Embodiment 10 | ????14 | ????40 | ????2709 | ????29 | ????157 |
| Embodiment 11 | ????13 | ????38 | ????2613 | ????31 | ????159 |
| Comparative Examples | ?????- | ????35 | ????2800 | ????28 | ????157 |
Claims (16)
1. hot-fusible high-molecular adhesive comprises:
Thermoplastics (parts by weight) 100
Peroxide initiator (parts by weight) 0.1～1.5
Polar monomer (parts by weight) 0.2～10
2. hotmelt according to claim 1 is characterized in that described thermoplastics is the polyolefine that contains tertiary carbon atom on the molecular chain.
3. as hotmelt as described in the claim 2, it is characterized in that described polyolefine is the polypropylene that contains tertiary carbon atom on the molecular chain.
4. as hotmelt as described in the claim 2, it is characterized in that described polyolefine is the polyethylene that contains tertiary carbon atom on the molecular chain.
5. hotmelt according to claim 1 is characterized in that the peroxide initiator is selected from dicumyl peroxide, peroxidized t-butyl perbenzoate or benzoyl peroxide, and its parts by weight are 0.3～1.
6. hotmelt according to claim 1 is characterized in that polar monomer is selected from unsaturated monoprotic acid, unsaturated dibasic acid or MALEIC ANHYDRIDE, and unsaturated monacid structural formula is:
Wherein R is C
1～C
5Alkyl;
The structural formula of unsaturated dibasic acid is:
R wherein
1, R
2Be respectively zero or C
1～C
3Alkyl;
The polar monomer parts by weight are 0.5～4.
7. as hotmelt as described in the claim 6, it is characterized in that the unsaturated monoprotic acid of described polar monomer is vinylformic acid.
8. as hotmelt as described in the claim 6, it is characterized in that described polar monomer unsaturated dibasic acid is a maleic acid.
9. hotmelt according to claim 1 is characterized in that this tackiness agent also contains the linking agent of 0.1～5 parts by weight.
10. as hotmelt as described in the claim 9, it is characterized in that described linking agent is selected from three tricarbimide triolefin lactones, liquid polybutadiene or Vinylstyrene, its parts by weight are
0.2～4。
11. as hotmelt one of as described in the claim 1～10, on the hotmelt thermoplastics molecular chain that it is characterized in that making grafting polar monomer, the melt flow rate (MFR) of hotmelt is greater than 10g/10min.
12. as hotmelt as described in the claim 11, the melt flow rate (MFR) that it is characterized in that hotmelt is greater than 15g/10min.
13. as hotmelt as described in the claim 11, the melt flow rate (MFR) that it is characterized in that hotmelt is greater than 30g/10min.
14. the preparation method of hotmelt comprises each component is mixed in high-speed mixer according to claim 1, adds then in the forcing machine, extruding pelletization makes this tackiness agent in 160～240 ℃ of temperature ranges.
15. the preparation method as hotmelt as described in the claim 14 is characterized in that mixing time is 2～10min in high-speed mixer, the extruder temperature scope is 180～230 ℃, and the extruder screw length-to-diameter ratio is more than or equal to 25.
16. hotmelt can be used for preparing organic filler and compound plastic plate according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98122120A CN1123613C (en) | 1998-12-03 | 1998-12-03 | Hot-fusible high-molecular adhesive and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98122120A CN1123613C (en) | 1998-12-03 | 1998-12-03 | Hot-fusible high-molecular adhesive and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1255523A true CN1255523A (en) | 2000-06-07 |
| CN1123613C CN1123613C (en) | 2003-10-08 |
Family
ID=5227600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98122120A Expired - Fee Related CN1123613C (en) | 1998-12-03 | 1998-12-03 | Hot-fusible high-molecular adhesive and its preparing process |
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| Country | Link |
|---|---|
| CN (1) | CN1123613C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302316B (en) * | 2008-06-16 | 2011-04-13 | 江苏新泉汽车饰件有限公司 | Production method of co-intercal type nano-polypropylene composite material |
| CN102153973A (en) * | 2011-05-25 | 2011-08-17 | 泰州市五行高分子材料科技有限公司 | Anti-corrosion adhesive for fire hose and preparation method thereof |
| CN103289598A (en) * | 2013-05-07 | 2013-09-11 | 安徽金门工贸有限公司 | Hot melt adhesive for composite boards and preparation method thereof |
| CN104710950A (en) * | 2013-09-13 | 2015-06-17 | 蒋云忠 | High-molecular bonding material for inorganic non-combustible safety grade aluminum composite board |
| CN110466035A (en) * | 2018-05-11 | 2019-11-19 | 临沂斯科瑞聚氨酯材料有限公司 | A kind of preparation method of the zero formaldehyde plate based on environmentally friendly glue |
| CN110539383A (en) * | 2018-05-29 | 2019-12-06 | 北京斯科瑞新材料科技股份有限公司 | Production method for preparing zero-formaldehyde regenerated board by using waste wood material |
| CN110903669A (en) * | 2018-09-18 | 2020-03-24 | 北京斯科瑞新材料科技股份有限公司 | Zero-formaldehyde regenerated board and preparation method thereof |
| CN110900779A (en) * | 2018-09-18 | 2020-03-24 | 北京斯科瑞新材料科技股份有限公司 | Zero-formaldehyde environment-friendly straw board and preparation method thereof |
| CN110936462A (en) * | 2018-09-21 | 2020-03-31 | 临沂斯科瑞聚氨酯材料有限公司 | Preparation method of zero-formaldehyde environment-friendly straw board based on environment-friendly water gel |
Families Citing this family (1)
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| CN103146311A (en) * | 2013-03-27 | 2013-06-12 | 南通市福来特化工有限公司 | Production method of high-molecular hot melting adhesive |
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| CN86104775B (en) * | 1986-07-14 | 1988-07-27 | 华中师范大学 | Preparation of polyolefin adhesive |
| ATE74368T1 (en) * | 1987-10-14 | 1992-04-15 | Rohm & Haas | POLYMER ADDITIVES FOR USE IN ADHESIVE COMPOSITIONS. |
| MY104107A (en) * | 1987-11-04 | 1993-12-31 | Mitsui Chemicals Incorporated | Adhesive resin compositions and laminates utilizing same |
| US4957974A (en) * | 1988-03-29 | 1990-09-18 | Rohm And Haas Company | Graft copolymers and blends thereof with polyolefins |
| DE69016711T2 (en) * | 1989-08-07 | 1995-07-13 | Mitsui Petrochemical Ind | Adhesive composition, laminate containing an adhesive layer made from this composition and process for its manufacture. |
| FR2657008B1 (en) * | 1990-01-12 | 1994-02-18 | Johnson Johnson Sa | |
| US5140074A (en) * | 1990-01-26 | 1992-08-18 | Himont Incorporated | Method of producing olefin polymer graft copolymers |
| IL99498A0 (en) * | 1990-10-05 | 1992-08-18 | Himont Inc | Blends of graft copolymers of propylene polymer material and of olefinic rubber material |
| IL102166A0 (en) * | 1991-06-21 | 1993-01-14 | Himont Inc | Grafting vinyl monomers on particulate olefin polymers |
| US5696203A (en) * | 1996-07-19 | 1997-12-09 | Montell North America Inc. | Process for producing polyolefin grafted copolymers |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101302316B (en) * | 2008-06-16 | 2011-04-13 | 江苏新泉汽车饰件有限公司 | Production method of co-intercal type nano-polypropylene composite material |
| CN102153973A (en) * | 2011-05-25 | 2011-08-17 | 泰州市五行高分子材料科技有限公司 | Anti-corrosion adhesive for fire hose and preparation method thereof |
| CN103289598A (en) * | 2013-05-07 | 2013-09-11 | 安徽金门工贸有限公司 | Hot melt adhesive for composite boards and preparation method thereof |
| CN103289598B (en) * | 2013-05-07 | 2016-04-20 | 安徽金门工贸有限公司 | A kind of composite sheet hot melt adhesive and preparation method thereof |
| CN104710950A (en) * | 2013-09-13 | 2015-06-17 | 蒋云忠 | High-molecular bonding material for inorganic non-combustible safety grade aluminum composite board |
| CN104710950B (en) * | 2013-09-13 | 2016-08-17 | 蒋云忠 | A kind of for the inorganic polymeric adhesion material not firing safe level aluminum composite plate |
| CN110466035A (en) * | 2018-05-11 | 2019-11-19 | 临沂斯科瑞聚氨酯材料有限公司 | A kind of preparation method of the zero formaldehyde plate based on environmentally friendly glue |
| CN110539383A (en) * | 2018-05-29 | 2019-12-06 | 北京斯科瑞新材料科技股份有限公司 | Production method for preparing zero-formaldehyde regenerated board by using waste wood material |
| CN110903669A (en) * | 2018-09-18 | 2020-03-24 | 北京斯科瑞新材料科技股份有限公司 | Zero-formaldehyde regenerated board and preparation method thereof |
| CN110900779A (en) * | 2018-09-18 | 2020-03-24 | 北京斯科瑞新材料科技股份有限公司 | Zero-formaldehyde environment-friendly straw board and preparation method thereof |
| CN110936462A (en) * | 2018-09-21 | 2020-03-31 | 临沂斯科瑞聚氨酯材料有限公司 | Preparation method of zero-formaldehyde environment-friendly straw board based on environment-friendly water gel |
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| Publication number | Publication date |
|---|---|
| CN1123613C (en) | 2003-10-08 |
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