CN109880551A - Without aldehyde fire-resistant binder and its preparation method and application, board-like material - Google Patents
Without aldehyde fire-resistant binder and its preparation method and application, board-like material Download PDFInfo
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Abstract
The present invention provides a kind of no aldehyde fire-resistant binders and its preparation method and application, board-like material, belong to adhesive techniques field.The present invention provides a kind of no aldehyde fire-resistant binders, are mainly made of raw material from the following weight: 40-80 parts of linear low density polyethylene, 15-40 parts of modified poly ethylene, 1-5 parts of thermoplastic polyurethane, 2-10 parts of polyolefin elastomer and 3-12 parts of fire retardant；Wherein, modified poly ethylene is the high density polyethylene (HDPE) and low density polyethylene (LDPE) of carboxylic unsaturated monomer graft modification.This has excellent flame retardant property without aldehyde fire-resistant binder, and adhesion strength is high, water-tolerant.The addition of polyolefin elastomer can reduce the polarity without aldehyde fire-resistant binder surface, improve wetting property, and then improve contact area, increase physical bonds (mechanical interlocked) power.The groups such as isocyanates and carbamate in thermoplastic polyurethane can form Van der Waals force with the hydroxyl on wood-cellulose, and then improve adhesive strength.
Description
Technical field
The invention belongs to adhesive techniques fields, and in particular to a kind of no aldehyde fire-resistant binder and preparation method thereof and answer
With, board-like material.
Background technique
Board-like material is one of big plate of wood-based plate three, the beginning in timber processing modernization period is indicated, for train, vapour
The effects of vehicle, aircraft, ship, building and packing case material.Board-like material can improve the comprehensive utilization ratio of timber, be to save timber
One main path.
Currently, what the board-like material of 80%-90% used is three-aldehyde glue without aldehyde fire-resistant binder, i.e. Lauxite, phenolic aldehyde
Resin and melamine are without aldehyde fire-resistant binder, current such no aldehyde fire-resistant binder adhesive property, cost control, production technology
And use is very mature, but have a large amount of Form aldehyde releases in the production and use process of this no aldehyde fire-resistant binder, it obtains
Board-like material finished product in have a large amount of residues of formaldehyde, release process slowly influences persistently.Another kind of more commonly used no aldehyde is fire-retardant
Binder is rubber made from soybean cake, and this no aldehyde fire-resistant binder is although formaldehydeless, but starch is easy mouldy or life in wet environment
Worm, while easily swelling of making moist, cause board-like material to be removed.It is polyurethane adhesive there are also a kind of no aldehyde fire-resistant binder, this no aldehyde
Fire-resistant binder is also formaldehydeless, but at high cost, and in process solvent volatilization so that smell is big.In addition, hot melt adhesive film
Also formaldehydeless and at low cost, but hot melt adhesive film easy firing, board-like material is not met to fire-retardant requirement, heat used at present
Melten gel film adhesive does not carry out flame retardant treatment, this also in that the addition meeting of fire retardant so that adhesive property is greatly reduced.
It is therefore desired to provide a kind of no aldehyde fire-resistant binder, it is able to solve at least one of above problem.
In consideration of it, the present invention is specifically proposed.
Summary of the invention
The first purpose of this invention is to provide a kind of no aldehyde fire-resistant binder, can overcome the above problem or at least
Partly solve above-mentioned technical problem.
Second object of the present invention is to provide the preparation method of above-mentioned no aldehyde fire-resistant binder.
Third object of the present invention is that providing no aldehyde fire-resistant binder is preparing the application in board-like material.
Fourth object of the present invention is to provide a kind of board-like material, and the board-like material is by above-mentioned no aldehyde flame-retardant adhesive
What agent or above-mentioned preparation method obtained bonds without aldehyde fire-resistant binder.
First aspect according to the present invention, provides a kind of no aldehyde fire-resistant binder, and the no aldehyde fire-resistant binder is main
It is made of raw material from the following weight:
40-80 parts of linear low density polyethylene, 15-40 parts of modified poly ethylene, 1-5 parts of thermoplastic polyurethane, polyolefin bullet
Property 2-10 parts of body and fire retardant 3-12 parts；
Wherein, the modified poly ethylene is the high density polyethylene (HDPE) and low-density of carboxylic unsaturated monomer graft modification
Polyethylene.
Preferably, the no aldehyde fire-resistant binder is mainly made of raw material from the following weight:
50-65 parts of linear low density polyethylene, 20-28 parts of modified poly ethylene, 1-3 parts of thermoplastic polyurethane, polyolefin bullet
Property 4-7 parts of body and fire retardant 8-12 parts.
Preferably, the no aldehyde fire-resistant binder is mainly made of raw material from the following weight:
58 parts of linear low density polyethylene, 25 parts of modified poly ethylene, 2 parts of thermoplastic polyurethane, 5 parts of polyolefin elastomer and
10 parts of fire retardant.
Preferably, the modified poly ethylene is mainly made of raw material from the following weight: 50-90 parts of high density polyethylene (HDPE),
It is 10-40 parts of low density polyethylene (LDPE), unsaturated monomer 0.1-3 parts and 0.01-0.5 parts of initiator carboxylic；
Preferably, the modified poly ethylene is mainly made of raw material from the following weight: 60-80 parts of high density polyethylene (HDPE),
It is 20-35 parts of low density polyethylene (LDPE), unsaturated monomer 0.5-1.5 parts and 0.1-0.3 parts of initiator carboxylic；
Preferably, the modified poly ethylene is mainly made of raw material from the following weight: 70 parts of high density polyethylene (HDPE), low close
30 parts of polyethylene of degree, 1 part of carboxylic unsaturated monomer and 0.2 part of initiator.
Preferably, the melt index of the high density polyethylene (HDPE) is 2-15g/10min；
And/or the melt index of the low density polyethylene (LDPE) is 1-20g/10min；
And/or the carboxylic unsaturated monomer is unsaturated carboxylic acid and/or unsaturated acid anhydride, preferably maleic acid
Acid anhydride and/or acrylic acid；
And/or the initiator is dibenzoyl peroxide and/or double two or five initiators.
Preferably, the raw material further includes 0.01-0.2 parts by weight antioxidant, preferably 0.05-0.15 parts by weight antioxygen
Agent, further preferably 0.1 parts by weight antioxidant；
Preferably, the antioxidant is Hinered phenols antioxidant, preferably hindered phenol type pentaerythritol ester kind antioxidant.
Preferably, the melt index of the linear low density polyethylene is 1-10g/min；
And/or the melt index of the thermoplastic polyurethane is 2-15g/min；
And/or the polyolefin elastomer is ethylene-butene copolymer and/or ethylene-octene copolymer, preferably second
Alkene-octene copolymer, further preferably octene mass percentage are the ethylene-octene copolymer of 30%-50%；
Preferably, the fire retardant includes halogenated flame retardant, preferably decabromodiphenylethane, eight bromo ether and tetrabromobisphenol A
At least one of.
The second aspect according to the present invention provides the preparation method of above-mentioned no aldehyde fire-resistant binder, comprising the following steps:
The raw material of above-mentioned no aldehyde fire-resistant binder is mixed, then squeezes out and obtains no aldehyde fire-resistant binder.
Preferably, the preparation method comprises the following steps:
(a) high density polyethylene (HDPE), low density polyethylene (LDPE), carboxylic unsaturated monomer and initiator are mixed, is then squeezed
Modified poly ethylene is obtained out；
(b) linear low density polyethylene, modified poly ethylene, thermoplastic polyurethane, polyolefin elastic made from step (a)
Body, fire retardant and antioxidant mix, and then squeeze out and obtain no aldehyde fire-resistant binder.
According to the present invention in terms of third, provides above-mentioned no aldehyde fire-resistant binder or above-mentioned preparation method obtains without aldehyde
Fire-resistant binder is preparing the application in board-like material.
4th aspect according to the present invention, provides a kind of board-like material, and the board-like material is fire-retardant viscous by above-mentioned no aldehyde
What knot agent or above-mentioned preparation method obtained bonds without aldehyde fire-resistant binder.
The present invention provides a kind of no aldehyde fire-resistant binder, this is without aldehyde fire-resistant binder by by the thermoplasticity of specific dosage
The coordinated effect of polyurethane, fire retardant, linear low density polyethylene, modified poly ethylene and polyolefin elastomer, is prepared into
Arrive without aldehyde fire-resistant binder without aldehyde, there is excellent flame retardant property, and adhesion strength is high, water-tolerant.Polyolefin elastomer
Addition can reduce the polarity without aldehyde fire-resistant binder surface, improve the wetting property without aldehyde fire-resistant binder, and then improve and connect
Contacting surface product, increases physical bonds (mechanical interlocked) power.The groups energy such as isocyanates and carbamate in thermoplastic polyurethane
Van der Waals force is formed with the hydroxyl on wood-cellulose, and then improves adhesive strength.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiments and examples, but this field skill
Art personnel will be understood that following embodiments and embodiment are merely to illustrate the present invention, and are not construed as limiting model of the invention
It encloses.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.The person that is not specified actual conditions, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
First aspect according to the present invention, provides a kind of no aldehyde fire-resistant binder, no aldehyde fire-resistant binder mainly by with
The raw material of lower parts by weight is made:
40-80 parts of linear low density polyethylene, 15-40 parts of modified poly ethylene, 1-5 parts of thermoplastic polyurethane, polyolefin bullet
Property 2-10 parts of body and fire retardant 3-12 parts；
Wherein, modified poly ethylene is the high density polyethylene (HDPE) and low density polyethylene of carboxylic unsaturated monomer graft modification
Alkene.
This without aldehyde fire-resistant binder by by the thermoplastic polyurethane of specific dosage, fire retardant, linear low density polyethylene,
The effect of the coordinated of modified poly ethylene and polyolefin elastomer, be prepared without aldehyde fire-resistant binder without aldehyde, have excellent
Flame retardant property, and adhesion strength is high, water-tolerant.The addition of polyolefin elastomer can be reduced without aldehyde fire-resistant binder surface
Polarity improves the wetting property without aldehyde fire-resistant binder, and then improves contact area, increases physical bonds (mechanical interlocked) power.
The groups such as isocyanates and carbamate in thermoplastic polyurethane can form Van der Waals force with the hydroxyl on wood-cellulose,
And then improve adhesive strength.
Linear low density polyethylene, abbreviation LLDPE are formed by ethylene and a small amount of alpha-olefin copolymer, and linea low density is poly-
The optional fusing point of ethylene is 110-125 DEG C, and the optional density of linear low density polyethylene is 0.91-0.94g/cm3, linear low close
The degree optional melt index of polyethylene is 1-10g/10min.Linear low density polyethylene is 40-80 parts, linear low density polyethylene
The typical but non-limiting parts by weight of alkene be 40 parts, 42 parts, 44 parts, 46 parts, 48 parts, 50 parts, 52 parts, 54 parts, 56 parts, 58 parts,
60 parts, 62 parts, 64 parts, 66 parts, 68 parts, 70 parts, 72 parts, 74 parts, 76 parts, 78 parts or 80 parts.Linear low density polyethylene is typical
But unrestricted melt index is 1g/min, 2g/min, 3g/min, 4g/min, 5g/min, 6g/min, 7g/min, 8g/
Min, 9g/min or 10g/min.
It should be noted that the condition of linear low density polyethylene melt index test is 190 DEG C, 2.16kg, test mark
Standard is ASTM D 1238.
Modified poly ethylene is the high density polyethylene (HDPE) and low density polyethylene (LDPE) of carboxylic unsaturated monomer graft modification, this
Locating modified poly ethylene is that the low density polyethylene (LDPE) of carboxylic unsaturated monomer graft modification and carboxylic unsaturated monomer connect
The modified high density polyethylene (HDPE) of branch.Carboxylic unsaturated monomer optionally unsaturated carboxylic acid and/or unsaturated acid anhydride.It is modified
Polyethylene is 15-40 parts, and the typical but non-limiting parts by weight of modified poly ethylene are 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24
Part, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts or 40 parts.
Thermoplastic polyurethane, abbreviation TPU are a kind of (AB)nType block linear polymer, A be high molecular weight (1000~
6000) polyester or polyethers, B are the glycol containing 2~12 carbons, and chemical structure is diisocyanate between AB segment, heat
The melt index of plastic polyurethane is optionally 2-15g/min；.Thermoplastic polyurethane be 1-5 part, thermoplastic polyurethane typical case but
Unrestricted parts by weight are 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts or 5 parts.Thermoplastic polyurethane allusion quotation
Type but unrestricted melt index are 2g/min, 3g/min, 4g/min, 5g/min, 6g/min, 7g/min, 8g/min, 9g/
Min, 10g/min, 11g/min, 12g/min, 13g/min, 14g/min or 15g/min.
It should be noted that the condition of thermoplastic polyurethane melt index test is 190 DEG C, 2.16kg.
Polyolefin elastomer is that ethylene is formed with alpha-olefine polymerizing, and optional alpha-olefin has butene-1, hexene -1, octene -
1, tetramethyl amylene -1 etc..The optional density of polyolefin elastomer is 0.85-0.89g/cm3.Polyolefin elastomer is optionally
Ethylene-butene copolymer and/or ethylene-octene copolymer.Polyolefin elastomer is 2-10 parts, and polyolefin elastomer is typical but non-
Restrictive parts by weight are 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts.
Fire retardant is additive flame retardant, optionally for halogenated flame retardant (organic chloride and organic bromide) and/or
Non-halogen fire retardant.Fire retardant is 3-12 parts, and the typical but non-limiting parts by weight of fire retardant are 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4
Part, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts or 10 parts.
As further preferred technical solution, no aldehyde fire-resistant binder is mainly made of raw material from the following weight:
50-65 parts of linear low density polyethylene, 20-28 parts of modified poly ethylene, 1-3 parts of thermoplastic polyurethane, polyolefin bullet
Property 4-7 parts of body and fire retardant 8-12 parts.
In the preferred embodiment, by reasonably adjusting and optimizing linear low density polyethylene, modified poly ethylene, heat
The dosage of plastic polyurethane, polyolefin elastomer and fire retardant, enables adhesive preferably to take into account anti-flammability and caking property.
As further preferred technical solution, no aldehyde fire-resistant binder is mainly made of raw material from the following weight:
58 parts of linear low density polyethylene, 25 parts of modified poly ethylene, 2 parts of thermoplastic polyurethane, 5 parts of polyolefin elastomer and
10 parts of fire retardant.
As further preferred technical solution, modified poly ethylene is mainly made of raw material from the following weight: high density
It is 50-90 parts of polyethylene, 10-40 parts of low density polyethylene (LDPE), unsaturated monomer 0.1-3 parts and initiator 0.01-0.5 carboxylic
Part.In the preferred embodiment, carboxylic unsaturated monomer initiator effect under be grafted on high density polyethylene (HDPE) and
On low density polyethylene (LDPE), grafting rate and polarity are helped to improve, the carboxylic being grafted on high density polyethylene (HDPE) and low density polyethylene (LDPE)
Base can react with the hydroxyl on fiber in timber, improve the adhesive property and water resistance of binder.
In a preferred embodiment, the optional melt index of high density polyethylene (HDPE) is 2-15g/10min.High density
The typical but non-limiting parts by weight of polyethylene are 50 parts, 52 parts, 54 parts, 56 parts, 58 parts, 60 parts, 62 parts, 64 parts, 66 parts, 68
Part, 70 parts, 72 parts, 74 parts, 76 parts, 78 parts, 80 parts, 82 parts, 84 parts, 86 parts, 88 parts or 90 parts.High density polyethylene (HDPE) it is typical but
Unrestricted melt index be 2g/10min, 4g/10min, 5g/10min, 6g/10min, 7g/10min, 10g/10min,
11g/10min, 12g/10min, 13g/10min, 14g/10min or 15g/10min.
It should be noted that the condition of high density polyethylene (HDPE) melt index test is 190 DEG C, 2.16kg.
In a preferred embodiment, the optional density of low density polyethylene (LDPE) is 0.91-0.94g/cm3, low-density
The optional melt index of polyethylene is 1-20g/10min.The typical but non-limiting parts by weight of low density polyethylene (LDPE) are 10 parts, 12
Part, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts or 40 parts.It is low
The typical but non-limiting melt index of density polyethylene is 1g/10min, 4g/10min, 5g/10min, 6g/10min, 7g/
10min、10g/10min、11g/10min、12g/10min、13g/10min、14g/10min、15g/10min、18g/10min、
19g/10min or 20g/10min.
It should be noted that the condition of low density polyethylene (LDPE) melt index test is 190 DEG C, 2.16kg.
In a preferred embodiment, carboxylic unsaturated monomer is chosen as unsaturated carboxylic acid and/or unsaturation
Acid anhydrides, the carboxylic typical but non-limiting parts by weight of unsaturated monomer be 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part,
0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts,
1.9 parts, 2.0 parts, 2.1 parts, 2.2 parts, 2.3 parts, 2.4 parts, 2.5 parts, 2.6 parts, 2.7 parts, 2.8 parts, 2.9 parts or 3.0 parts.
In a preferred embodiment, carboxylic unsaturated monomer is maleic anhydride and/or acrylic acid.It is grafted with
The polyethylene of maleic anhydride or acrylic acid can react with the hydroxyl on cellulose in timber, make it have good water resistance
Energy.
In a preferred embodiment, initiator is chosen as dibenzoyl peroxide and/or double two or five initiators.Draw
Send out the typical but non-limiting parts by weight of agent be 0.01 part, 0.05 part, 0.1 part, 0.15 part, 0.2 part, 0.25 part, 0.3 part,
0.35 part, 0.4 part, 0.45 part or 0.5 part.In the preferred embodiment, dibenzoyl peroxide or double two or five initiators
Carboxylic unsaturated monomer can be effectively facilitated to be grafted on high density polyethylene (HDPE) and low density polyethylene (LDPE), contained so that being grafted with
Carboxyl in the high density polyethylene (HDPE) and low density polyethylene (LDPE) of carboxyl unsaturated monomer can react with the hydroxyl on timber,
Improve the water resistance without aldehyde fire-resistant binder.
As further preferred technical solution, modified poly ethylene is mainly made of raw material from the following weight: high density
It is 60-80 parts of polyethylene, 20-35 parts of low density polyethylene (LDPE), unsaturated monomer 0.5-1.5 parts and initiator 0.1-0.3 carboxylic
Part.
As further preferred technical solution, modified poly ethylene is mainly made of raw material from the following weight: high density
70 parts of polyethylene, 30 parts of low density polyethylene (LDPE), 1 part of carboxylic unsaturated monomer and 0.2 part of initiator.
As further preferred technical solution, raw material further includes 0.01-0.2 parts by weight antioxidant, and antioxidant can be effective
Extend the service life of binder.Preferably, antioxidant is 0.05-0.15 parts by weight, preferably 0.1 parts by weight.Antioxidant allusion quotation
Type but unrestricted parts by weight are 0.01 part, 0.02 part, 0.04 part, 0.06 part, 0.08 part, 0.1 part, 0.12 part, 0.14 part,
0.16 part, 0.18 part or 0.2 part.
In a preferred embodiment, antioxidant is Hinered phenols antioxidant, preferably hindered phenol type pentaerythrite
Esters antioxidant, hindered phenol type pentaerythritol ester kind antioxidant can effectively extend the service life of binder.
As further preferred technical solution, polyolefin elastomer is ethylene-butene copolymer and/or ethylene-octene
Copolymer.In the preferred embodiment, ethylene-butene copolymer and/or ethylene-octene copolymer have wellability, can
Effectively improve adhesive speed and physical bond intensity.
As further preferred technical solution, polyolefin elastomer is ethylene-octene copolymer, preferably octene quality
Percentage composition is the ethylene-octene copolymer of 30%-50%.
As further preferred technical solution, fire retardant includes halogenated flame retardant, preferably decabromodiphenylethane, eight bromines
At least one of ether and tetrabromobisphenol A.
The second aspect according to the present invention provides the preparation method of above-mentioned no aldehyde fire-resistant binder, comprising the following steps:
The raw material of above-mentioned no aldehyde fire-resistant binder is mixed, then squeezes out and obtains no aldehyde fire-resistant binder.
Then the present invention squeezes out by mixing each raw material, no aldehyde fire-resistant binder can be prepared.Process flow letter
It is single, easy to operate, easy to implement, processing raw material sources it is wide, it is economical and easily available, be nontoxic, environment-friendly type raw material.The present invention to environment,
Place, equipment etc. are without specifically limited, and used low in raw material price, safety and environmental protection performance is good, low for equipment requirements, investment at
This is low, practicability and adaptable, be a kind of environmental protection, energy conservation, high efficiency and low cost without aldehyde fire-resistant binder preparation method, can
To realize the production of a large amount, application easy to spread at a lower cost.
It should be noted that the present invention does not have special limitation to the mode of extrusion, it is ripe using those skilled in the art institute
The extrusion way known squeezes out.It such as can be twin-screw extrusion, be also possible to single screw rod extrusion.
It should be noted that the present invention does not have special limitation to the mode of mixing, it is ripe using those skilled in the art institute
The blending manner known.It such as can be high-speed mixer to be mixed, be also possible to by the way of mixing or mixing.
As further preferred technical solution, preparation method the following steps are included:
(a) high density polyethylene (HDPE), low density polyethylene (LDPE), carboxylic unsaturated monomer and initiator are mixed, is then squeezed
Modified poly ethylene is obtained out；
(b) linear low density polyethylene, modified poly ethylene, thermoplastic polyurethane, polyolefin elastic made from step (a)
Body, fire retardant and antioxidant mix, and then squeeze out and obtain no aldehyde fire-resistant binder.
In step (a), the temperature of extrusion is 50-180 DEG C, and/or, screw speed 200-400rpm, preferably 250-
320rpm.In step (b), the temperature of extrusion is 50-180 DEG C, and/or, screw speed 200-400rpm, preferably 250-
320rpm。
The temperature of extruder is divided into 8-12 sections, and feed zone temperature is 50 DEG C, and with the direction of Flow of Goods and Materials, temperature gradually increases
Add, finally, the temperature of discharge port is 180 DEG C.
According to the present invention in terms of third, provides above-mentioned no aldehyde fire-resistant binder or above-mentioned preparation method obtains without aldehyde
Fire-resistant binder is preparing the application in board-like material.
The binder has both excellent flame retardant property and adhesive property, applies in board-like material, can improve plate
Its adhesive property is kept while Flame Retardancy energy.
4th aspect according to the present invention, provides a kind of board-like material, board-like material is by above-mentioned no aldehyde fire-resistant binder
Or being bonded without aldehyde fire-resistant binder of obtaining of above-mentioned preparation method.
There is excellent flame retardant property, and the adhesion strength of board-like material by the board-like material that the binder bonds
It is high.
Technical solution of the present invention is described further below in conjunction with embodiment and comparative example.
Embodiment 1
1, binder
A kind of no aldehyde fire-resistant binder, is mainly made of raw material from the following weight:
58 parts of linear low density polyethylene (LLDPE), 25 parts of modified poly ethylene, 2 parts of thermoplastic polyurethane (TPU), polyene
5 parts of olefin elastomer (POE), 10 parts of fire retardant and 0.1 part of antioxidant.
The trade mark of linear low density polyethylene is LLDPE7144, and the trade mark of thermoplastic polyurethane is 8670AU, polyolefin bullet
Property body the trade mark be POE8137, fire retardant is decabromodiphenylethane, and antioxidant is antioxidant 1010.
Wherein, modified poly ethylene is mainly made of raw material from the following weight: 70 parts of high density polyethylene (HDPE) (HDPE), low close
Degree 30 parts of polyethylene (LDPE), 1 part of carboxylic unsaturated monomer and 0.2 part of initiator.
The trade mark of high density polyethylene (HDPE) is HD5675, and the trade mark of low density polyethylene (LDPE) is LD605, carboxylic unsaturated single
Body is acrylic acid, and initiator is dibenzoyl peroxide.
2, the preparation without aldehyde fire-resistant binder
(1) high density polyethylene (HDPE), low density polyethylene (LDPE), carboxylic unsaturated monomer and initiator are mixed, it is then sharp
Modified poly ethylene is obtained with twin-screw extrusion；Extrusion temperature is 50-180 DEG C, and (extruder is divided into 10 sections of progress temperature controls, by feed zone
To mouth mold, temperature is successively increased, be followed successively by from feed zone to mouth mold 60 DEG C, 130 DEG C, 160 DEG C, 160 DEG C, 170 DEG C, 170 DEG C,
175 DEG C, 175 DEG C, 180 DEG C, 175 DEG C), screw speed 400rpm.
(2) by linear low density polyethylene, modified poly ethylene, thermoplastic polyurethane, polyolefin elastomer, fire retardant and anti-
Oxygen agent mixes, and then obtains no aldehyde fire-resistant binder using twin-screw extrusion；Extrusion temperature is 110-180 DEG C, and (extruder is divided into
10 sections of progress temperature controls, by feed zone to mouth mold, temperature is successively increased, and 110 DEG C, 150 DEG C, 160 are followed successively by from feed zone to mouth mold
DEG C, 165 DEG C, 170 DEG C, 170 DEG C, 175 DEG C, 175 DEG C, 180 DEG C, 175 DEG C), screw speed 400rpm.
Embodiment 2
Embodiment 2-10 difference from example 1 is that, the dosage of each raw material of binder is different, the type of each raw material
Same as Example 1, specific as shown in table 1, unit is parts by weight.
The dosage of each raw material in 1 embodiment 2-10 of table
| LLDPE | Modified poly ethylene | TPU | POE | Fire retardant | Antioxidant | |
| Embodiment 2 | 40 | 40 | 1 | 10 | 3 | 0.01 |
| Embodiment 3 | 80 | 15 | 5 | 2 | 12 | 0.2 |
| Embodiment 4 | 50 | 28 | 1 | 7 | 8 | 0.15 |
| Embodiment 5 | 65 | 20 | 3 | 4 | 12 | 0.05 |
| Embodiment 6 | — | — | 1 | — | — | — |
| Embodiment 7 | — | — | 3 | — | — | — |
| Embodiment 8 | — | — | 5 | — | — | — |
| Embodiment 9 | — | 15 | — | — | — | — |
| Embodiment 10 | — | 40 | — | — | — | — |
In table 1, "-" indicates identical as the dosage in embodiment 1.
Embodiment 11
Embodiment 11 difference from example 1 is that, embodiment 11 do not contain antioxidant dibenzoyl peroxide.
Embodiment 12-13
Embodiment 12 and 13 difference from example 1 is that, the dosage of each raw material of binder is different, modified poly ethylene
Raw material dosage it is different, specifically as shown in table 2 and table 3, unit is parts by weight.
The dosage of 2 each raw material of the binder of embodiment 12 and 13 of table
| LLDPE | Modified poly ethylene | TPU | POE | Fire retardant | Antioxidant | |
| Embodiment 12 | 63 | 20 | 4 | 3 | 10 | 0.1 |
| Embodiment 13 | 46 | 35 | 1 | 7 | 11 | 0.1 |
The raw material dosage of 3 modified poly ethylene of embodiment 12 and 13 of table
| HDPE | LDPE | Acrylic acid | Dibenzoyl peroxide | |
| Embodiment 12 | 78 | 22 | 3 | 0.5 |
| Embodiment 13 | 72 | 28 | 0.1 | 0.01 |
Comparative example 1
Comparative example 1 difference from example 1 is that, in comparative example 1 thermoplastic polyurethane be 8 parts.
Comparative example 2
Comparative example 2 difference from example 1 is that, in comparative example 2 thermoplastic polyurethane be 0.5 part.
Comparative example 3
Comparative example 3 difference from example 1 is that, in comparative example 3 modified poly ethylene be 10 parts.
Comparative example 4
Comparative example 4 difference from example 1 is that, in comparative example 4 modified poly ethylene be 50 parts.
Test example 1
To the melt index, density, breaking strength, fracture of embodiment 1-13 and comparative example the 1-4 binder being prepared
Elongation, flame retardant rating, bonding strength and burst size of methanal are characterized, and obtain that the results are shown in Table 4.Wherein, melting refers to
The condition of number test is 190 DEG C, 2.16kg；Density measurement standard is ASTM D792；Tensile property testing standard is ASTM
D412, the testing standard of flame retardant rating are GB/T2408-2008, and the testing standard of bonding strength is GB/T17657-2013.
In the testing standard GB/T2408-2008 of flame retardant rating, V2 indicates to carry out sample 10 seconds twice combustion testings
Afterwards, flame extinguishes in 30 seconds.The absorbent cotton that can be ignited below 30cm.V1 indicates to carry out sample 10 seconds twice combustion testings
Afterwards, flame extinguishes in 30 seconds.The absorbent cotton that cannot be ignited below 30cm.V0 indicates to carry out sample 10 seconds twice combustion testings
Afterwards, flame extinguishes in 10 seconds.There cannot be comburant to fall down.
The performance of table 4 embodiment 1-13 and comparative example 1-4 binder
The burst size of methanal of embodiment 1-13 is 0mg/m2·h.The application is free of formaldehyde without aldehyde fire-resistant binder.
Experimental example 2
Raw material: Eucalyptus veneer (thick 1.8mm × long 350mm × wide 350mm；Moisture content 10%)；Adhering resin film is (thick
0.045mm × long 350mm × wide 350mm).
Operating procedure: taking an Eucalyptus veneer is bottom plate, spreads adhering resin film made from an embodiment, takes second
Eucalyptus veneer is opened, the fiber direction vertical with bottom plate fiber is chosen and mats formation, it is thin to be then covered with adhering resin made from an embodiment
Film takes third Eucalyptus veneer, chooses fiber and mats formation with second vertical direction of veneer fiber, mat formation and finish, carries out hot pressing
Molding, later cold pressing sizing.Hot pressing condition are as follows: 180 DEG C of temperature；Pressure 0.6MPa；Time 5min.Cold pressing condition are as follows: temperature 25
℃；Pressure 0.2MPa；Time 2min.
Bonding strength of the table 5 without aldehyde fire-resistant binder
| Bonding strength MPa | Bonding strength MPa | ||
| Embodiment 1 | 2.3 | Embodiment 10 | 2.4 |
| Embodiment 2 | 1.7 | Embodiment 11 | 2.1 |
| Embodiment 3 | 1.6 | Embodiment 12 | 2.2 |
| Embodiment 4 | 1.7 | Embodiment 13 | 1.8 |
| Embodiment 5 | 2.2 | Comparative example 1 | 1.4 |
| Embodiment 6 | 1.6 | Comparative example 2 | 0.9 |
| Embodiment 7 | 2.3 | Comparative example 3 | 1.1 |
| Embodiment 8 | 2.2 | Comparative example 4 | 1.6 |
| Embodiment 9 | 1.8 |
Test result shows that adhering resin paint burst size of methanal of the invention reaches national E0 standard, and bonding strength reaches
The common board-like material national standard of II class.Meanwhile suitable fire retardant and suitable polyurethane can arrange in pairs or groups use, it can be effective simultaneous
Care for the adhesive property and flame retardant property of resin.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of no aldehyde fire-resistant binder, which is characterized in that the no aldehyde fire-resistant binder is mainly by the raw material of following parts by weight
It is made:
40-80 parts of linear low density polyethylene, 15-40 parts of modified poly ethylene, 1-5 parts of thermoplastic polyurethane, polyolefin elastomer
2-10 parts and fire retardant 3-12 parts；
Wherein, the modified poly ethylene is the high density polyethylene (HDPE) and low density polyethylene of carboxylic unsaturated monomer graft modification
Alkene.
2. no aldehyde fire-resistant binder according to claim 1, which is characterized in that the no aldehyde fire-resistant binder mainly by with
The raw material of lower parts by weight is made:
50-65 parts of linear low density polyethylene, 20-28 parts of modified poly ethylene, 1-3 parts of thermoplastic polyurethane, polyolefin elastomer
4-7 parts and fire retardant 8-12 parts.
3. no aldehyde fire-resistant binder according to claim 1, which is characterized in that the no aldehyde fire-resistant binder mainly by with
The raw material of lower parts by weight is made:
58 parts of linear low density polyethylene, 25 parts of modified poly ethylene, 2 parts of thermoplastic polyurethane, 5 parts of polyolefin elastomer and fire-retardant
10 parts of agent.
4. no aldehyde fire-resistant binder according to claim 1, which is characterized in that the modified poly ethylene is mainly by following heavy
The raw material of amount part is made: 50-90 parts of high density polyethylene (HDPE), 10-40 parts of low density polyethylene (LDPE), carboxylic unsaturated monomer 0.1-
3 parts and initiator 0.01-0.5 parts；
Preferably, the modified poly ethylene is mainly made of raw material from the following weight: 60-80 parts of high density polyethylene (HDPE), low close
Degree polyethylene 20-35 parts, it is unsaturated monomer 0.5-1.5 parts and 0.1-0.3 parts of initiator carboxylic；
Preferably, the modified poly ethylene is mainly made of raw material from the following weight: 70 parts of high density polyethylene (HDPE), low-density are poly-
30 parts of ethylene, 1 part of carboxylic unsaturated monomer and 0.2 part of initiator.
5. no aldehyde fire-resistant binder according to claim 4, which is characterized in that the melt index of the high density polyethylene (HDPE)
For 2-15g/10min；
And/or the melt index of the low density polyethylene (LDPE) is 1-20g/10min；
And/or the carboxylic unsaturated monomer be unsaturated carboxylic acid and/or unsaturated acid anhydride, preferably maleic anhydride and/
Or acrylic acid；
And/or the initiator is dibenzoyl peroxide and/or double two or five initiators.
6. no aldehyde fire-resistant binder according to claim 1-5, which is characterized in that the raw material further includes
0.01-0.2 parts by weight antioxidant, preferably 0.05-0.15 parts by weight antioxidant, further preferably 0.1 parts by weight antioxidant；
Preferably, the antioxidant is Hinered phenols antioxidant, preferably hindered phenol type pentaerythritol ester kind antioxidant.
7. no aldehyde fire-resistant binder according to claim 1-5, which is characterized in that the linear low density polyethylene
The melt index of alkene is 1-10g/min；
And/or the melt index of the thermoplastic polyurethane is 2-15g/min；
And/or the polyolefin elastomer is ethylene-butene copolymer and/or ethylene-octene copolymer, preferably ethylene-is pungent
Alkene copolymer, further preferably octene mass percentage are the ethylene-octene copolymer of 30%-50%；
Preferably, the fire retardant includes halogenated flame retardant, preferably in decabromodiphenylethane, eight bromo ether and tetrabromobisphenol A
It is at least one.
8. the preparation method of the described in any item no aldehyde fire-resistant binders of claim 1-7, which is characterized in that including following step
It is rapid:
The raw material of the described in any item no aldehyde fire-resistant binders of claim 1-7 is mixed, then it is fire-retardant viscous to obtain no aldehyde for extrusion
Tie agent；
Preferably, the preparation method comprises the following steps:
(a) high density polyethylene (HDPE), low density polyethylene (LDPE), carboxylic unsaturated monomer and initiator are mixed, is then squeezed out
To modified poly ethylene；
(b) linear low density polyethylene, modified poly ethylene, thermoplastic polyurethane, polyolefin elastomer, resistance made from step (a)
It fires agent and antioxidant mixes, then squeeze out and obtain no aldehyde fire-resistant binder.
9. the nothing that the described in any item no aldehyde fire-resistant binders of claim 1-7 or preparation method according to any one of claims 8 obtain
Aldehyde fire-resistant binder is preparing the application in board-like material.
10. a kind of board-like material, which is characterized in that the board-like material is fire-retardant by the described in any item no aldehyde of claim 1-7
What binder or preparation method according to any one of claims 8 obtained bonds without aldehyde fire-resistant binder.
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| CN104449470A (en) * | 2014-12-12 | 2015-03-25 | 广州市合诚化学有限公司 | Adhesive resin for barrier composite hose and preparation method and application thereof |
| CN107868630A (en) * | 2017-09-17 | 2018-04-03 | 河源市普立隆新材料科技有限公司 | A kind of adhering resin with barriers function and preparation method thereof |
| CN107995997A (en) * | 2016-03-31 | 2018-05-04 | 古河电气工业株式会社 | Semiconductor machining bonding sheet |
| CN109337611A (en) * | 2018-10-17 | 2019-02-15 | 河源市普立隆新材料科技有限公司 | Aldehyde-free by wood adhering resin and preparation method |
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2019
- 2019-03-05 CN CN201910169940.6A patent/CN109880551A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449470A (en) * | 2014-12-12 | 2015-03-25 | 广州市合诚化学有限公司 | Adhesive resin for barrier composite hose and preparation method and application thereof |
| CN107995997A (en) * | 2016-03-31 | 2018-05-04 | 古河电气工业株式会社 | Semiconductor machining bonding sheet |
| CN107868630A (en) * | 2017-09-17 | 2018-04-03 | 河源市普立隆新材料科技有限公司 | A kind of adhering resin with barriers function and preparation method thereof |
| CN109337611A (en) * | 2018-10-17 | 2019-02-15 | 河源市普立隆新材料科技有限公司 | Aldehyde-free by wood adhering resin and preparation method |
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