WO2025031416A1 - Modified saccharide substance, treatment agent, preparation method therefor and use thereof - Google Patents

Abstract

A modified saccharide substance, a treatment agent, a preparation method therefor and the use thereof. The modified saccharide substance comprises a saccharide substance and an organosilicon polymer, wherein the saccharide substance is linked to the organosilicon polymer by means of a chemical bond, and the organosilicon polymer comprises a structural unit produced by a monomer I. The modified saccharide substance and the treatment agent containing same can be used in a wider pH environment, and can be used for treating various articles so as to endow the surfaces of the articles with oil- and water- repellent properties.

Description

Modified sugar substances, treating agents and preparation methods and applications thereof

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the priority of Chinese patent application with application number 202310988994.1 filed on August 7, 2023, and invention name “Modified sugar substances, treatment agents, preparation methods and applications thereof”. The entire contents of the above patent application are incorporated into this application as a whole.

Technical Field

The present application relates to a modified sugar substance, a treating agent, and a preparation method and application thereof.

Technical Background

The surface of paper, fiber fabrics, etc. is treated to make them water-repellent and oil-repellent, so that they can obtain some special application functions, such as paper can be used to package greasy foods, and fiber fabrics can prevent various stains well, thereby improving the cleanliness of clothes, etc. For a long time, in order to obtain this water-repellent and oil-repellent function, fluoride is generally used to treat paper, fiber fabrics, etc., which can make the surface of the object water-repellent and oil-repellent without changing the appearance of the object.

However, in recent years, due to the increasing attention of the international community to polyfluoroalkyl compounds (PFAS), in March 2023, the European Chemicals Agency (ECHA) launched a public consultation on the proposal submitted by Denmark, Germany, the Netherlands, Norway and Sweden to ECHA to add restrictions on the manufacture, marketing and use of PFAS in the REACH Restriction Chapter (REACH Annex XIVII), with the aim of giving relevant parties the opportunity to comment on the inclusion of PFAS in the REACH Restriction Chapter for control. After the public consultation, ECHA's Risk Assessment Committee (RAC) and Socio-Economic Analysis Committee (SEAC) will evaluate the proposed restrictions and form opinions based on the consultation opinions, and the European Commission will ultimately decide whether to include PFAS in the Restriction Chapter for control.

In view of the above situation, some new non-fluorine compounds are proposed to replace the existing fluorine-containing finishing agents.

Patent CN100300612 describes an organosiloxane copolymer that can be used for paper treatment to make the paper water- and oil-repellent. However, this copolymer is based on a coating method, and this coating requires film formation and the process is relatively complicated.

CN 114573768 B describes an organosilicon copolymer that can be used for treating articles. This copolymer is a cationic copolymer and has certain limitations in application, especially in alkaline environments where it may fail.

In modern industrial applications, alkaline environments, especially those with high pH values, are more common. For example, in the modern papermaking industry, alkaline papermaking is the mainstream process. For example, in the leather kneading process, alkaline environments are more common. Another example is the treatment of stone. Since marble is mainly composed of calcium carbonate, it will react with acid, so it is particularly important to ensure that the chemical still maintains its function in alkaline conditions. Therefore, it is necessary to develop a treatment agent that is suitable for a wider range of pH values.

Summary of the invention

The purpose of the present application is to provide a modified sugar substance that can be polymerized in water. The modified sugar substance and the treating agent comprising the modified sugar substance can be used in a wider pH environment to treat a variety of objects, thereby giving the surface of the objects oil and water repellent properties.

In a first aspect, the present application provides a modified carbohydrate substance, which includes a carbohydrate substance and an organosilicon polymer, wherein the carbohydrate substance and the organosilicon polymer are connected by a chemical bond, and the organosilicon polymer includes a structural unit produced by a monomer I, wherein the general structural formula of the monomer I is shown in Formula I:

MZ or ZMZ

Formula I

Wherein, M contains a polymerizable functional group;

Z is selected from the following structures,

In Z, R ₃ is each independently selected from a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₀ aryl group, a C ₇ -C ₁₂ aralkyl group, a C ₇ -C ₁₂ alkaryl group, a C ₁ -C ₂₀ alkoxy group or an R ₄ -OR ₅ - group, R ₄ is a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₀ aryl group, a C ₇ -C ₁₂ aralkyl group or a C ₇ -C ₁₂ alkaryl group, R ₅ is a C ₁ -C ₂₀ alkylene group, and 1≤a≤200;

_Y1 and _Y2 are the same or different, and are independently selected from _C1 - _C20 alkyl, _C6 - _C20 aryl, _C7 - _C12 aralkyl, _C7 - _C12 alkaryl or the following structure (1):

_R7 is each independently selected from a _C1 - _C20 alkyl group, a _C6 - _C20 aryl group, a _C7 - _C12 aralkyl group or a _C7 - _C12 alkaryl group; _R8 is each independently selected from a _C1 - _C20 alkyl group, _{a C6} - _C20 aryl group, a _C7 - _C12 aralkyl group, a _C7 - _C12 alkaryl group, a _C1 - _C20 alkoxy group or an _R9 - _OR10- group, wherein _R9 is a _C1 - _C20 alkyl group, a _C6 - _C20 aryl group, a _C7 - _C12 aralkyl group or a _C7 - _C12 alkaryl group, _{and R10} is a _C1 - _C20 alkylene group, and 0≤b≤200.

In some embodiments, the organosilicon polymer is grafted onto the saccharide substance.

In some embodiments, the polymerizable functional group in M is selected from a group containing a carbon-carbon double bond.

In some embodiments, in Formula I, M is as shown in Formula I-1:

_CH2 ＝C( _R1 )-XB-

I-1

In formula I-1, _R1 is selected from a hydrogen atom or a _C1 - _C20 alkyl group; B is selected from a _C1 - _C20 alkylene group, a _C6 - _C20 arylene group, and a combination thereof;

X is selected from the group represented by X-1 and X-2,

-C(O)-O-

X-1

-C(O)-N(R ₂ )-

X-2

R ₂ is selected from a hydrogen atom or a C ₁ -C ₂₀ alkyl group.

In some embodiments, in Formula I-1, _R1 is selected from a hydrogen atom or a _C1 - _C10 alkyl group, such as a C1 _{- C3} alkyl group, a _C4 - _C6 alkyl group, or a _C8 - _C10 alkyl group. In some embodiments, in Formula I-1, B is a _C1 - _C10 alkylene group, such as a _C1 - _C3 alkylene group, a _C4 - _C6 alkylene group, or a _C8 - _C10 alkylene group.

In some embodiments, in Formula I-1, B is a C ₆ -C ₁₅ arylene group, for example, a C ₆ -C ₉ arylene group, a C ₁₀ -C ₁₂ arylene group, or a C ₁₃ -C ₁₅ arylene group.

In some embodiments, in the groups represented by X-1 and X-2, R ₂ is selected from a hydrogen atom or a C ₁ -C ₁₀ alkyl group, for example, a C ₁ -C ₃ alkyl group, a C ₄ -C ₆ alkyl group, or a C ₈ -C ₁₀ alkyl group.

In some embodiments, in Formula I-1, R ₁ is selected from a hydrogen atom or a methyl group; B is a C ₁ -C ₆ alkylene group; and in X, R ₂ is selected from a hydrogen atom or a methyl group.

In some embodiments, in Formula I, M is as shown in Formula I-2:
_CH2 ＝C( _R1 )-WB-
I-2

In formula I-2, R ₁ is selected from a hydrogen atom or a C ₁ -C ₂₀ alkyl group;

W is selected from the group represented by W-1, W-2, W-3 and W-4,

-OC(O)-N(R ₂ )- W-2
-OC(O)-O- W-3
-OC(O)-ODN(R ₂ )- W-4

_R2 is selected from a hydrogen atom or a _C1 - _C20 alkyl group, D is a _C1 - _C20 alkylene group; when W is selected from W-1, B is absent or is a _C1 - _C20 alkylene group, when W is selected from W-2, W-3, W-4, B is selected from a _C1 - _C20 alkylene group, a _C6 - _C20 arylene group and a combination thereof.

In some embodiments, in formula I-2, _R1 is selected from a hydrogen atom or a _C1 - _C10 alkyl group, such as a C1 _{- C3} alkyl group, a _C4 - _C6 alkyl group, or a _C8 - _C10 alkyl group. In some embodiments, in formula I-2, B is a _C1 - _C10 alkylene group, such as a _C1 - _C3 alkylene group, a _C4 - _C6 alkylene group, or a _C8 - _C10 alkylene group.

In some embodiments, in formula I-2, _R2 is selected from a hydrogen atom or a _C1 - _C10 alkyl group, such as a C1 _{- C3} alkyl group, a _C4 - _C6 alkyl group, or a _C8 - _C10 alkyl group. In some embodiments, in formula I-2, D is a _C1 - _C10 alkylene group, such as a _C1 - _C3 alkylene group, a _C4 - _C6 alkylene group, or a _C8 - _C10 alkylene group.

In some embodiments, in Formula I-2, R ₁ and R ₂ are selected from hydrogen atoms or methyl groups, and B and D are C ₁ -C ₆ alkylene groups.

In some embodiments, when W is selected from W-1, B is absent or is a C ₁ -C ₁₀ alkylene group, for example, a C ₁ -C ₃ alkylene group, a C ₄ -C ₆ alkylene group, or a C ₈ -C ₁₀ alkylene group.

In some embodiments, when W is selected from W-2, W-3, and W-4, B is a C ₁ -C ₁₀ alkylene group, for example, a C ₁ -C ₃ alkylene group, a C ₄ -C ₆ alkylene group, or a C ₈ -C ₁₀ alkylene group.

In some embodiments, when W is selected from W-2, W-3, and W-4, B is a C ₆ -C ₁₅ arylene group, for example, a C ₆ -C ₉ arylene group, a C ₁₀ -C ₁₂ arylene group, or a C ₁₃ -C ₁₅ arylene group.

In some embodiments, in Formula I, M is as shown in Formula I-3:

In formula I-3, R ₁ is selected from a hydrogen atom or a C ₁ -C ₂₀ alkyl group, and B is independently selected from a C ₁ -C ₂₀ alkylene group, a C ₆ -C ₂₀ arylene group, and a combination thereof.

In some embodiments, in formula I-3, _R1 is selected from a hydrogen atom or a _C1 - _C10 alkyl group, such as a C1 _{- C3} alkyl group, a _C4 - _C6 alkyl group, or a _C8 - _C10 alkyl group. In some embodiments, in formula I-3, B is a _C1 - _C10 alkylene group, such as a _C1 - _C3 alkylene group, a _C4 - _C6 alkylene group, or a _C8 - _C10 alkylene group.

In some embodiments, in Formula I-3, B is a C ₆ -C ₁₅ arylene group, for example, a C ₆ -C ₉ arylene group, a C ₁₀ -C ₁₂ arylene group, or a C ₁₃ -C ₁₅ arylene group.

In some embodiments, in Formula I-3, R ₁ is selected from a hydrogen atom or a methyl group.

In some embodiments, in Z, _R3 is independently _C1 - _C10 alkyl, _C6 - _C10 aryl, _C7 - _C12 aralkyl, _C7 - _C12 alkaryl, _C1 - _C10 alkoxy or _R4 - _OR5 -group, _R4 is _C1 - _C10 alkyl, _C6 - _C10 aryl, _C7 - _C12 aralkyl or _C7 - _C12 alkaryl, _R5 is _C1 - _C10 alkylene, 1≤a≤100; _R7 is independently _C1 - _C10 alkyl, _C6 - _C10 aryl, _C7 - _C12 aralkyl or _C7 - _C12 alkaryl; _R8 is independently _C1 - _C10 alkyl, _C6 - _C10 aryl, _C7 -C12 R 9 is a C 1 -C ₁₂ aralkyl group, a C ₇ -C ₁₂ alkaryl group, a C ₁ -C ₁₀ alkoxy group or a R ₉ -OR ₁₀ - group, wherein R ₉ is a C ₁ -C ₁₀ alkyl group, a C ₆ -C ₁₀ aryl group, a C ₇ -C ₁₂ aralkyl group or a C ₇ -C ₁₂ alkaryl group, R ₁₀ is a C ₁ -C ₁₀ alkylene group, and 0≤b≤100.

In some embodiments, in Z, _R3 is each independently a _C1 - _C6 alkyl, a _C6 - _C10 aryl, a _C7 - _C10 aralkyl, a _C7 - _C10 alkaryl, a _C1 - _C6 alkoxyl group or an _R4 - _OR5 -group, _R4 is a _C1 - _C6 alkyl, a _C6 - _C10 aryl, a _C7 - _C10 aralkyl or a _C7 - _C10 alkaryl, _R5 is a _C1 - _C6 alkylene group, 1≤a≤30; _R7 is each independently a _C1 - _C6 alkyl, a _C6 - _C10 aryl, a _C7 - _C10 aralkyl or a _C7 - _C10 alkaryl; _R8 is each independently a _C1 - _C6 alkyl, a C6-C10 aryl, a _C7 - _C10 aralkyl or a _C7 -C10 alkaryl R ₉ is a C ₁ -C ₆ alkyl, a C ₆ -C ₁₀ aryl, a C _{7 -C 10 aralkyl} or _{a C 7 -C 10 alkaryl ,} and R _{10 is} a _{C 1 -C 16 alkylene} group, and _0≤b≤30 .

In some embodiments, a is an integer of 1-80, an integer of 1-30, an integer of 1-20, or an integer of 1-10.

In some embodiments, b is 0. In some embodiments, b is an integer from 1-30, an integer from 1-20, an integer from 1-10, or an integer from 1-5.

In some embodiments, Z is independently selected from one or more of the following structures i-1 to i-6:

R is each independently selected from a C ₁ -C ₁₀ alkyl group, a C ₆ -C ₁₀ aryl group, a C ₇ -C ₁₂ aralkyl group or a C _{7 -C} 12 alkaryl group;

1≤m+1≤60, preferably 1≤m+1≤30; 0≤p≤60, preferably 0≤p≤30; 0≤q≤60, preferably 0≤q≤30; 1≤x≤9, preferably 1≤x≤7, and each x may be the same or different.

In some embodiments, R is a C ₁ -C ₃ alkyl group, such as methyl.

In some embodiments, Z is selected from

One or more of;

R is each independently selected from a C ₁ -C ₁₀ alkyl group, a C ₆ -C ₁₀ aryl group, a C ₇ -C ₁₂ aralkyl group or a C ₇ -C ₁₂ alkaryl group;

Me represents methyl, ph represents phenyl; 1≤m+1≤60, preferably 1≤m+1≤30; 0≤p≤60, preferably 0≤p≤30; 0≤q≤60, preferably 0≤q≤30; 1≤x≤9, preferably 1≤x≤7, and each x may be the same or different.

In some embodiments, m is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9.

In some embodiments, x is 1, 2, 3, 4, 5, 6, or 7.

In some embodiments, monomer I is selected from

CH ₂ =C(CH ₃ )C(O)-O-(CH ₂ ) ₃ Si(OSi(CH ₃ ) ₃ ) ₃ ;

CH ₂ =CHC(O)-O-(CH ₂ ) ₃ Si(OSi(CH ₃ ) ₃ ) ₃ ;

CH ₂ =C(CH ₃ )C(O)-O-(CH ₂ ) ₃ Si(CH ₃ )(OSi(CH ₃ ) ₃ ) ₂ ;

CH ₂ =CHC(O)-O-(CH ₂ ) ₃ Si(CH ₃ )(OSi(CH ₃ ) ₃ ) ₂ ;

CH ₂ =C(CH ₃ )C(O)-NH-(CH ₂ ) ₃ Si(OSi(CH ₃ ) ₃ ) ₃ ;

CH ₂ =CHC(O)-NH-(CH ₂ ) ₃ Si(OSi(CH ₃ ) ₃ ) ₃ ;

CH ₂ =C(CH ₃ )C(O)-NH-(CH ₂ ) ₃ Si(CH ₃ )(OSi(CH ₃ ) ₃ ) ₂ ;

CH ₂ =CHC(O)-NH-(CH ₂ ) ₃ Si(CH ₃ )(OSi(CH ₃ ) ₃ ) ₂ ;

CH ₂ =C(CH ₃ )C(O)-O-(CH ₂ ) ₃ Si(OSi(CH ₂ CH ₃ ) ₃ ) ₃ ;

CH ₂ =CHC(O)-O-(CH ₂ ) ₃ Si(OSi(CH ₂ CH ₃ ) ₃ ) ₃ ;

CH ₂ =C(CH ₃ )C(O)-O-CH ₂ -Si(OSi(CH ₃ ) ₃ ) ₃ ;

CH ₂ =C(CH ₃ )C(O)-O-(CH ₂ ) ₃ Si(CH ₃ )[O-[Si(CH ₃ ) ₂ O]n-Si(CH ₃ ) ₂ C ₄ H ₉ ] ₂ , 0≤n≤25;

CH ₂ =C(CH ₃ )C(O)-O-(CH ₂ ) ₃ [Si(CH ₃ ) ₂ O]n-Si(CH ₃ ) ₂ C ₄ H ₉ , 1≤n≤25;

CH ₂ =C(CH ₃ )C(O)-O-(CH ₂ ) ₃ [Si(CH ₃ ) ₂ O]n-Si(CH ₃ ) ₂ C ₈ H ₁₇ , 1≤n≤25;

CH ₂ =C(CH ₃ )C(O)-O-(CH ₂ ) ₃ [Si(CH ₃ ) ₂ O]n-Si(CH ₃ ) ₃ , 1≤n≤25;

CH ₂ =CH-ph-Si(OSi(CH ₃ ) ₃ ) ₃ (ph means );

CH ₂ =CH-ph-(CH ₂ ) ₂ Si(OSi(CH ₃ ) ₃ ) ₃ (ph means );

CH ₂ ＝CH-ph-(CH ₂ ) ₃ [Si(CH ₃ ) ₂ O]n-Si(CH ₃ ) ₂ C ₄ H ₉ (C ₄ H ₉ represents a butyl group, ph represents ), 1≤n≤25;

CH ₂ =CH-OC(O)-NH-(CH ₂ ) ₃ Si(OSi(CH ₃ ) ₃ ) ₃ ;

CH ₂ ＝CH-OC(O)-NH-(CH ₂ ) ₃ -[Si(CH ₃ ) ₂ O]n-Si(CH ₃ ) ₂ C ₄ H ₉ (C ₄ H ₉ represents a butyl group), 1≤n≤25;

CH ₂ =CH-OC(O)-O-(CH ₂ ) ₃ -Si(OSi(CH ₃ ) ₃ ) ₃ ;

CH ₂ ＝CH-OC(O)-O-(CH ₂ ) ₃ -[Si(CH ₃ ) ₂ O]n-Si(CH ₃ ) ₂ C ₄ H ₉ (C ₄ H ₉ represents a butyl group), 1≤n≤25;

CH ₂ =CH-OC(O)-O-(CH ₂ ) ₂ -NH-(CH ₂ ) ₃ Si(OSi(CH ₃ ) ₃ ) ₃ ;

CH ₂ ＝CH-OC(O)-O-(CH ₂ ) ₂ -NH-(CH ₂ ) ₃ [Si(CH ₃ ) ₂ O]n-Si(CH ₃ ) ₂ C ₄ H ₉ (C ₄ H ₉ represents a butyl group), 1≤n≤25;

CH ₂ =CH-C(O)-N[-(CH ₂ ) ₃ -Si(OSi(CH ₃ ) ₃ ) ₃ ] ₂ ;

CH ₂ =CH-C(O)-N[-(CH ₂ ) ₃ -Si(CH ₃ )(OSi(CH ₃ ) ₃ ) ₂ ] ₂ ;

CH ₂ ＝CH—C(O)—N[—(CH ₂ ) ₃ —(Si(CH ₃ ) ₂ O) _n —Si(CH ₃ ) ₂ C ₄ H ₉ ] ₂ (C ₄ H ₉ represents a butyl group), 1≤n≤25;

CH ₂ ＝C(CH ₃ )-C(O)-N[-(CH ₂ ) ₃ -(Si(CH ₃ ) ₂ O) _n -Si(CH ₃ ) ₂ C ₄ H ₉ ] ₂ (C ₄ H ₉ represents a butyl group), 1≤n≤ 25.

In some embodiments, monomer I includes silicon monomer I-A and/or silicon monomer I-B;

The general formula of the silicon monomer IA is the same as that of formula I, and also satisfies the following conditions: when a is 1, _Y1 and/or _Y2 are structures of formula (1); when a is greater than 1 and ≤ 200, at least one _Y1 is a structure of formula (1) and/or at least one _Y2 is a structure of formula (1);

The general formula of silicon monomer IB is the same as formula I, and also satisfies that _Y1 and _Y2 are the same or different, and are independently selected from _C1 - _C20 alkyl, _C6 - _C20 aryl, _C7 - _C12 aralkyl and _C7 - _C12 alkaryl.

In some embodiments, the general formula of silicon monomer I-A is as shown in Formula I-A:

MZ ₁ or Z ₁ -MZ ₁

Formula I-A

Wherein, M contains a polymerizable functional group;

Z ₁ is selected from the following structures,

In Z ₁ , R ₃ is each independently selected from a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₀ aryl group, a C ₇ -C ₁₂ aralkyl group, a C ₇ -C ₁₂ alkaryl group, a C ₁ -C ₂₀ alkoxy group or an R ₄ -OR ₅ - group, R ₄ is a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₀ aryl group, a C ₇ -C ₁₂ aralkyl group or a C ₇ -C ₁₂ alkaryl group, R ₅ is a C ₁ -C ₂₀ alkylene group, and 1≤a≤200;

_Y1 and _Y2 are the same or different, and are independently selected from _C1 - _C20 alkyl, _C6 - _C20 aryl, _C7 - _C12 aralkyl, _C7 - _C12 alkylaryl and the following structure of formula (1), provided that when a is 1, _Y1 and/or _Y2 are the structure of formula (1), and when a is greater than 1 and ≤200, at least one _Y1 is the structure of formula (1) and/or at least one _Y2 is the structure of formula (1):

_R7 is each independently selected from a _C1 - _C20 alkyl group, a _C6 - _C20 aryl group, a _C7 - _C12 aralkyl group or a _C7 - _C12 alkaryl group; _R8 is each independently selected from a _C1 - _C20 alkyl group, _{a C6} - _C20 aryl group, a _C7 - _C12 aralkyl group, a _C7 - _C12 alkaryl group, a _C1 - _C20 alkoxy group or an _R9 - _OR10- group, wherein _R9 is a _C1 - _C20 alkyl group, a _C6 - _C20 aryl group, a _C7 - _C12 aralkyl group or a _C7 - _C12 alkaryl group, _{and R10} is a _C1 - _C20 alkylene group, and 0≤b≤200.

In the present application, the definition of M in Formula I-A is the same as the definition of M in Formula I.

In some embodiments, in _Z1 , _R3 is independently C1- _C10 alkyl, _C6 - _C10 aryl, _C7 - _C12 aralkyl, _C7 - _C12 alkaryl, C1- _C10 alkoxy or _R4 - _OR5 -group, _R4 is _C1 - _C10 alkyl, _C6 - _C10 aryl, _{C7 - C12} aralkyl or _C7 - _C12 alkaryl, _R5 is C1- _C10 alkylene, 1≤a≤100; _R7 is independently _C1 - _C10 alkyl, _{C6-C10 aryl} , _C7 - _C12 aralkyl or _C7 - _C12 alkaryl; _R8 is independently _{C1 -C10 alkyl} , _{C6 - C10} aryl, C7- _C12 -C ₁₂ aralkyl, C ₇ -C ₁₂ alkaryl, C ₁ -C ₁₀ alkoxy or R ₉ -OR ₁₀ - group, wherein R ₉ is C ₁ -C ₁₀ alkyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₂ aralkyl or C ₇ -C ₁₂ alkaryl, R ₁₀ is C ₁ -C ₁₀ alkylene, and/or 0≤b≤80.

According to some embodiments of the present invention, in _Z1 , _R3 are each independently _C1 - _C6 alkyl, _C6 - _C10 aryl, _C7 - _C10 aralkyl, _C7 - _C10 alkaryl, _C1 - _C6 alkoxy or _R4 - _OR5 -group, _R4 is _C1 - _C6 alkyl, _C6 - _C10 aryl, _C7 - _C10 aralkyl or _C7 - _C10 alkaryl, _R5 is _C1 - _C6 alkylene, 1≤a≤30; _R7 is each independently _C1 - _C6 alkyl, _C6 - _C10 aryl, _C7 - _C10 aralkyl or _C7 - _C10 alkaryl; _R8 is each independently _C1 - _C6 alkyl, _C6 - _C10 aryl, _C7 - _C10 aralkyl, _C7 - _C10 alkaryl, _C1 - _C6 alkoxy or _R9 - _OR10 -group; - group, wherein R ₉ is a C ₁ -C ₆ alkyl group, a C ₆ -C ₁₀ aryl group, a C ₇ -C ₁₀ aralkyl group or a C ₇ -C ₁₀ alkaryl group, R ₁₀ is a C ₁ -C ₁₆ alkylene group, and 0≤b≤30.

In some embodiments, in Formula I-A, a is an integer of 1-80, an integer of 1-30, an integer of 1-20, or an integer of 1-10.

In some embodiments, in Formula I-A, b is 0. In some embodiments, in Formula I-A, b is an integer of 1-30, an integer of 1-20, an integer of 1-10, or an integer of 1-5.

In some embodiments, Z ₁ is selected from one or more of the following structures i-3 to i-6:

R is each independently selected from a C ₁ -C ₁₀ alkyl group, a C ₆ -C ₁₀ aryl group, a C ₇ -C ₁₂ aralkyl group or a C ₇ -C ₁₂ alkaryl group;

1≤m+1≤60, preferably 1≤m+1≤30; 0≤p≤60, preferably 0≤p≤30; 0≤q≤60, preferably 0≤q≤30; 1≤x≤9, preferably 1≤x≤7, and each x may be the same or different.

In some embodiments, R is a C ₁ -C ₃ alkyl group, such as methyl.

In some preferred embodiments, Z ₁ is selected from the following structures:

One or more of;

Me represents a methyl group, 1≤m+1≤60, preferably 1≤m+1≤30; 0≤p≤60, preferably 0≤p≤30; 0≤q≤60, preferably 0≤q≤30; 1≤x≤9, preferably 1≤x≤7, and each x may be the same or different.

In some embodiments, the silicon monomer I-A is selected from

CH ₂ =C(CH ₃ )C(O)-O-(CH ₂ ) ₃ Si(OSi(CH ₃ ) ₃ ) ₃ ;

CH ₂ =CHC(O)-O-(CH ₂ ) ₃ Si(OSi(CH ₃ ) ₃ ) ₃ ;

CH ₂ =C(CH ₃ )C(O)-O-(CH ₂ ) ₃ Si(CH ₃ )(OSi(CH ₃ ) ₃ ) ₂ ;

CH ₂ =CHC(O)-O-(CH ₂ ) ₃ Si(CH ₃ )(OSi(CH ₃ ) ₃ ) ₂ ;

CH ₂ =C(CH ₃ )C(O)-NH-(CH ₂ ) ₃ Si(OSi(CH ₃ ) ₃ ) ₃ ;

CH ₂ =CHC(O)-NH-(CH ₂ ) ₃ Si(OSi(CH ₃ ) ₃ ) ₃ ;

CH ₂ =C(CH ₃ )C(O)-NH-(CH ₂ ) ₃ Si(CH ₃ )(OSi(CH ₃ ) ₃ ) ₂ ;

CH ₂ =CHC(O)-NH-(CH ₂ ) ₃ Si(CH ₃ )(OSi(CH ₃ ) ₃ ) ₂ ;

CH ₂ =C(CH ₃ )C(O)-O-(CH ₂ ) ₃ Si(OSi(CH ₂ CH ₃ ) ₃ ) ₃ ;

CH ₂ =CHC(O)-O-(CH ₂ ) ₃ Si(OSi(CH ₂ CH ₃ ) ₃ ) ₃ ;

CH ₂ =C(CH ₃ )C(O)-O-CH ₂ -Si(OSi(CH ₃ ) ₃ ) ₃ ;

CH ₂ =C(CH ₃ )C(O)-O-(CH ₂ ) ₃ Si(CH ₃ )[O-[Si(CH ₃ ) ₂ O]n-Si(CH ₃ ) ₂ C ₄ H ₉ ] ₂ , 0≤n≤25;

CH ₂ =CH-ph-Si(OSi(CH ₃ ) ₃ ) ₃ (ph means );

CH ₂ =CH-ph-(CH ₂ ) ₂ Si(OSi(CH ₃ ) ₃ ) ₃ (ph means );

CH ₂ =CH-OC(O)-NH-(CH ₂ ) ₃ Si(OSi(CH ₃ ) ₃ ) ₃ ;

CH ₂ =CH-OC(O)-O-(CH ₂ ) ₃ -Si(OSi(CH ₃ ) ₃ ) ₃ ;

CH ₂ =CH-OC(O)-O-(CH ₂ ) ₂ -NH-(CH ₂ ) ₃ Si(OSi(CH ₃ ) ₃ ) _3;

CH ₂ =CH-C(O)-N[-(CH ₂ ) ₃ -Si(OSi(CH ₃ ) ₃ ) ₃ ] ₂ ;

CH ₂ =CH-C(O)-N[-(CH ₂ ) ₃ -Si(CH ₃ )(OSi(CH ₃ ) ₃ ) ₂ ] ₂ .

In some embodiments, the general formula of silicon monomer I-B is as shown in Formula I-B:

MZ ₂ or Z ₂ -MZ ₂

Formula I-B

Wherein, M contains a polymerizable functional group;

Z ₂ is selected from the following structures,

In _Z2 , _Y1 and _Y2 are the same or different and are each independently selected from a _C1 - _C20 alkyl group, a _C6 - _C20 aryl group, a _C7 - _C12 aralkyl group and a _C7 - _C12 alkaryl group; _R3 is each independently selected from a _C1 - _C20 alkyl group, a _C6 - _C20 aryl group, a _C7 - _C12 aralkyl group, a _C7 - _C12 alkaryl group, a _C1 - _C20 alkoxy group or an _R4 - _OR5- group, _R4 is a _C1 - _C20 alkyl group, a _C6 - _C20 aryl group, a _C7 - _C12 aralkyl group or a _C7 - _C12 alkaryl group, _R5 is a _C1 - _C20 alkylene group, and 1≤a≤200.

In the present application, the definition of M in Formula I-B is the same as the definition of M in Formula I.

In some embodiments, in _Z2 , _Y1 and _Y2 are the same or different, and are each independently selected from a _{C1-C10 alkyl} group, a _C6 - _C10 aryl group, a _C7 - _C12 aralkyl group, and a _C7 - _C12 alkaryl group; _R3 is each independently selected from a _C1 - _C10 alkyl group, a _C6 - _C12 aryl group, a _C7 - _C12 aralkyl group, a _C7 - _C12 alkaryl group, a _C1 - _C10 alkoxy group, or an _R4 - _OR5- group, _R4 is a _C1 - _C10 alkyl group, a _C6 - _C12 aryl group, a _C7 - _C12 aralkyl group, or a _C7 - _C12 alkaryl group, and _R5 is a _C1 - _C10 alkylene group.

According to some embodiments of the invention, in Z ₂ , 1≤a≤80. According to some embodiments of the invention, in Z ₂ , 1≤a≤30. According to some embodiments of the invention, in Z ₂ , 1≤a≤20. According to some embodiments of the invention, in Z ₂ , 1≤a≤10.

In some embodiments, in _Z2 , _Y1 and _Y2 are the same or different, and are each independently selected from _C1 - _C6 alkyl, _C6 - _C10 aryl, _C7 -C10 aralkyl and _C7 - _C10 alkaryl; _R3 is each independently selected from _C1 - _C6 alkyl, _C6 - _C10 aryl, _C7 - _C10 aralkyl, _C7 - _C10 alkaryl, _C1 - _C6 alkoxy or _R4 - _OR5 -group, _R4 is _C1 - _C6 alkyl _{, C6} - _C10 aryl, _C7 - _C10 aralkyl or _C7 - _C10 alkaryl, and _R5 is _C1 - _C6 alkylene.

In some embodiments, _Z2 is selected from one or more of the following structures i-1 to i-2:

R is each independently selected from C ₁ -C ₁₀ alkyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₂ aralkyl or C ₇ -C ₁₂ alkaryl;

1≤m+1≤60, preferably 1≤m+1≤30; 1≤x≤9, preferably 1≤x≤7.

_Z2 is preferably selected from the following structures:

One or more of;

Me represents a methyl group, ph represents a phenyl group; 1≤m+1≤60, preferably 1≤m+1≤30; 1≤x≤9, preferably 1≤x≤7.

In some embodiments, silicon monomer I-B is selected from

CH ₂ =C(CH ₃ )C(O)-O-(CH ₂ ) ₃ [Si(CH ₃ ) ₂ O]n-Si(CH ₃ ) ₂ C ₄ H ₉ (C ₄ H ₉ represents a butyl group), 1≤n≤25;

CH ₂ =C(CH ₃ )C(O)-O-(CH ₂ ) ₃ [Si(CH ₃ ) ₂ O]n-Si(CH ₃ ) ₂ C ₈ H ₁₇ , 1≤n≤25;

CH ₂ =C(CH ₃ )C(O)-O-(CH ₂ ) ₃ [Si(CH ₃ ) ₂ O]n-Si(CH ₃ ) ₃ , 1≤n≤25;

CH ₂ ＝CH-ph-(CH ₂ ) ₃ [Si(CH ₃ ) ₂ O]n-Si(CH ₃ ) ₂ C ₄ H ₉ (C ₄ H ₉ represents a butyl group, ph represents ), 1≤n≤25;

CH ₂ ＝CH-OC(O)-NH-(CH ₂ ) ₃ -[Si(CH ₃ ) ₂ O]n-Si(CH ₃ ) ₂ C ₄ H ₉ (C ₄ H ₉ represents a butyl group), 1≤n≤25;

CH ₂ ＝CH-OC(O)-O-(CH ₂ ) ₃ -[Si(CH ₃ ) ₂ O]n-Si(CH ₃ ) ₂ C ₄ H ₉ (C ₄ H ₉ represents a butyl group), 1≤n≤25;

CH ₂ ＝CH-OC(O)-O-(CH ₂ ) ₂ -NH-(CH ₂ ) ₃ [Si(CH ₃ ) ₂ O]n-Si(CH ₃ ) ₂ C ₄ H ₉ (C ₄ H ₉ represents a butyl group), 1≤n≤25;

CH ₂ ＝CH—C(O)—N[—(CH ₂ ) ₃ —(Si(CH ₃ ) ₂ O) _n —Si(CH ₃ ) ₂ C ₄ H ₉ ] ₂ (C ₄ H ₉ represents a butyl group), 1≤n≤25;

CH ₂ =C(CH ₃ )-C(O)-N[-(CH ₂ ) ₃ -(Si(CH ₃ ) ₂ O) _n -Si(CH ₃ ) ₂ C ₄ H ₉ ] ₂ (C ₄ H ₉ represents a butyl group), 1≤n≤25.

In some embodiments, the organosilicon polymer further comprises a structural unit produced by monomer III, wherein monomer III is a monomer having an anion supplying group and a polymerizable unsaturated group, and the anion supplying group is a carboxyl group or a sulfonic acid group.

In some embodiments, the polymerizable unsaturated group in monomer III is selected from a group containing a carbon-carbon double bond.

In some embodiments, monomer III is selected from (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, 2-acrylamide-2-methylpropanesulfonic acid, vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, vinylbenzenesulfonic acid, acrylamide-tert-butylsulfonic acid or salts thereof.

In some embodiments, the carbohydrate material is selected from one or more of starch materials, cellulose materials, galactomannan materials, xanthan gum materials, alginate materials, pectin materials, chitosan materials, gum arabic materials, carrageenan materials, agar materials and gellan gum materials.

In some embodiments, the weight average molecular weight of the carbohydrate substance is 1000-65000.

In some embodiments, the carbohydrate material is selected from starch materials, and the starch material is selected from one or more of starch, modified starch, degraded starch and modified degraded starch.

The starch in the present application can be obtained from all starch types, for example from potato, corn, wheat, rice, cassava, sorghum or waxy starch, the waxy starch having more than 80%, preferably more than 95% amylopectin, such as waxy corn starch or waxy potato starch. The starch can be modified anionically and/or cationic, esterified, Etherification and/or cross-linking.

In some embodiments, the modified starch is selected from one or more of cationic modified starch, anionic modified starch, and nonionic modified starch.

In some embodiments, the molecular weight Mw of starch is more suitably in the range of 1000-65000 Daltons. If the molecular weight is too large, it can be obtained by degrading or modifying the starch. The molar mass Mw of the degraded starch is preferably in the range of 2500-35000.

In some embodiments, in the modified starch, the ratio of cationic or anionic groups is specified by the degree of substitution (DS), which is, for example, 0.005-1.0, preferably 0.01-0.4.

Conventional cationized starches are prepared, for example, by reacting natural starches, such as potato, wheat, corn, rice or tapioca starch, with at least one quaternary ammonium compound.

According to some embodiments of the polymer of the present application, the carbohydrate substance is preferably starch, especially modified degraded starch, starch with a Mw molecular weight of 1000-65000.

In some embodiments, the mass content of the structural unit produced by monomer I in the organosilicon polymer is 5%-100%, for example, 5%, 10%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98% or any two thereof. In some embodiments, the mass content of the structural unit produced by monomer I in the organosilicon polymer is 30%-75%. In some embodiments, the mass content of the structural unit produced by monomer I in the organosilicon polymer is 40%-60%.

In some embodiments, the mass content of the mass of the carbohydrate in the modified carbohydrate is 5%-90%, for example, 5%, 10%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 88% or any two of them. In some embodiments, the mass content of the mass of the carbohydrate in the modified carbohydrate is 20%-70%. In some embodiments, the mass content of the mass of the carbohydrate in the modified carbohydrate is 30%-60%.

In some embodiments, the mass content of the structural unit produced by monomer III in the organosilicon polymer is 0.5%-30%, for example, 1%, 3%, 5%, 7%, 10%, 11%, 13%, 15%, 17%, 20%, 21%, 23%, 25%, 27% or any two thereof. In some embodiments, the mass content of the structural unit produced by monomer III in the organosilicon polymer is 3%-20%. In some embodiments, the mass content of the structural unit produced by monomer III in the organosilicon polymer is 5%-15%.

In a second aspect, the present application provides a treating agent, which comprises the modified sugar substance described in the first aspect, an optional emulsifier and an aqueous medium.

In some embodiments, the aqueous medium includes water and an optional organic solvent. In some embodiments, the aqueous medium is preferably water. In some embodiments, the aqueous medium includes water and an organic solvent. As the organic solvent herein, there is no particular limitation, and organic solvents that can be mixed with water are all applicable to the present application, and examples of organic solvents can be acetone, methyl ethyl ketone, ethyl acetate, ethanol, isopropanol, butyl diglycol, propylene glycol, dipropylene glycol, tripropylene glycol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, etc. It should be noted that the ratio of water to organic solvent is not particularly limited.

In some embodiments, the emulsifier is selected from one or more of a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant.

In some embodiments, the emulsifier is selected from the reaction products of long chain monohydric alcohols (C10-C22 alkanols) with 4-50 moles of ethylene oxide and/or propylene oxide per mole of alcohol, or ethoxylated phenols or alkoxylated alcohols esterified with sulfuric acid, which are usually used in a base-neutralized form.

In some embodiments, the emulsifier is selected from sodium alkane sulfonate, sodium alkyl sulfate, sodium dodecylbenzene sulfonate, sulfosuccinate, alkyl quaternary ammonium salts, alkyl benzyl ammonium salts (e.g., dimethyl C12-C18 alkyl benzyl ammonium chloride), primary, secondary or tertiary fatty amine salts, quaternary aminoamine compounds, alkyl pyridinium salts, alkyl oxazolium salts.

In a third aspect, the present application provides a method for preparing the treating agent described in the second aspect, which comprises: The polymerization reaction is carried out in the presence of a substance and an initiator.

In some embodiments, the preparation method comprises the following steps:

(1) mixing a sugar substance and water to obtain a first mixture;

(2) Adding monomers, initiators, optional organic solvents, optional emulsifiers and optional molecular weight regulators to the first mixture to carry out polymerization reaction.

According to some embodiments of the present application, the method for preparing the treating agent comprises the following steps:

Sugar substances and water are added into a reactor. After the temperature is raised to a certain level, the sugar substances are dispersed or dissolved in the water. Then, polymerizable monomer I and/or monomer III are gradually added dropwise or all added into the reactor. At the same time, an initiator is added dropwise to initiate polymerization, and finally a treating agent is obtained.

In a fourth aspect, the present application provides the use of the modified sugar substance described in the first aspect, the treating agent described in the second aspect, or the treating agent prepared by the method described in the third aspect in fiber fabrics, leather, non-woven fabrics, asbestos, fur, concrete, natural stone, paper products or plastics.

In a fifth aspect, the present application provides a water- and oil-repellent product, which includes a product and the modified sugar substance described in the first aspect or the treating agent described in the second aspect or the treating agent prepared by the method described in the third aspect, wherein the product is fiber fabric, leather, non-woven fabric, asbestos, fur, concrete, natural stone, paper product or plastic.

In some embodiments, the modified sugar substance described in the first aspect or the treating agent described in the second aspect or the treating agent prepared by the method described in the third aspect is attached to the surface and/or interior of the product.

In a sixth aspect, the present application provides a method for treating a product, comprising contacting the product with the modified sugar substance described in the first aspect or the treating agent described in the second aspect or the treating agent prepared by the method described in the third aspect, wherein the product is fiber fabric, leather, non-woven fabric, asbestos, fur, concrete, natural stone, paper product or plastic.

In some embodiments, the contacting is achieved by an internal addition process, a surface sizing process, a surface coating process, or an immersion treatment process.

In the present application, fiber fabrics include animal or plant natural fibers such as cotton, linen, wool, silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fiber, carbon fiber, asbestos fiber, or their mixed fiber fabrics.

Effects of the Invention

The modified sugar substance and the treating agent comprising the modified sugar substance of the present application can be used to treat a variety of articles including paper products, fiber fabrics, leather, non-woven fabrics, asbestos, fur, concrete, stone or plastic, and can impart water and oil repellency to the surface of the articles.

Specific implementation method:

In order to make the purpose, technical scheme and advantages of the present application clearer, the present application is further described in detail below in conjunction with the embodiments. These embodiments are only used to explain the present application and are not intended to constitute any limitation to the present application. The actual protection scope of the present application is set forth in the claims.

In this application, unless otherwise specified, the terms used have the general meanings known to those skilled in the art.

In the present application, the term "alkyl" refers to a straight chain alkyl or a branched alkyl, non-limiting examples of which include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, etc.

In the present application, the term "alkylene" refers to a straight chain alkylene or a branched chain alkylene, and non-limiting examples thereof include: methylene, ethylene, n-propylene, n-butylene, n-pentylene, -CHCH ₃ CH ₂ -, -CHCH ₃ CH ₂ CH ₂ -, CH ₂ CH ₃ CHCH ₂ -etc.

In this application, unless otherwise specified, "%" refers to mass percentage.

1. Aggregation method:

According to the present application, the treating agent comprising a modified saccharide is obtained by subjecting an olefin-containing unsaturated monomer to free radical emulsion polymerization in the presence of at least one redox initiator and a saccharide polymer, wherein

(a) 5% to 80% of monomer I, containing monomers of M-Z and or Z-M-Z structure,

(b) 5% to 80% of at least one carbohydrate having a Mw of 1000 to 65000, preferably a starch;

(c) 5% to 10% of monomer III, containing a polymerizable double bond structure and a hydrophilic functional group, such as acrylic acid;

The sum of I+sugar substances+III is 100%.

Preferred modified carbohydrate materials or treatment agents use the following components:

The carbohydrate material is preferably starch, which can be obtained from all starch types, for example from potato, corn, wheat, rice, cassava, sorghum or waxy starch, the waxy starch having more than 80%, preferably more than 95% amylopectin, such as waxy corn starch or waxy potato starch. The starch can be modified, esterified, etherified and/or crosslinked in anionic and/or cationic manner. Non-ionized starch, anionic or cationic starch is preferred.

The molecular weight Mw of starch is more suitably in the range of 1000-65000 Daltons. If the molecular weight is too large, it can be obtained by degrading or modifying the starch. The molar mass Mw of the degraded starch is preferably in the range of 2500-35000.

In the substituted starch, the proportion of cationic or anionic groups is defined by the degree of substitution (DS). The degree of substitution is, for example, 0.005-1.0, preferably 0.01-0.4.

All starches can be used. Conventional cationized starches are prepared, for example, by reacting natural starches, such as potato, wheat, corn, rice or tapioca starch, with at least one quaternary ammonium compound. The degradation of the starch is preferably carried out before the polymerization of the monomers, but can also be carried out during the polymerization of the monomers. The degradation can be carried out oxidatively, thermally, acidolytically or enzymatically. The degradation of the starch is preferably carried out enzymatically and/or oxidatively in the apparatus to be polymerized or in a separate step directly before the start of the emulsion polymerization. In the polymerization, a single degraded starch or a mixture of two or more degraded starches can be used. In the monomer reaction mixture containing several components, the starch is present in an amount of 5 to 90%, preferably 20 to 70%.

According to the present application, a redox initiator is used to initiate the polymerization reaction, and the initiator preferably contains a grafted water-soluble redox system, for example, comprising hydrogen peroxide and a heavy metal salt, or comprising hydrogen peroxide and sulfur dioxide, or comprising hydrogen peroxide and sodium metabisulfite. Other suitable redox systems are the following combinations: tert-butyl hydroperoxide/sulfur dioxide, potassium persulfate or sodium persulfate/sodium bisulfite, ammonium persulfate/sodium bisulfite, or ammonium persulfate/iron (II) sulfate. Preferably, a combination of hydrogen peroxide and a heavy metal salt such as iron (II) sulfate is used. Typically, the redox system additionally contains other reducing agents, such as ascorbic acid, formaldehyde sulfoxylate, yellow bisulfite or sodium dithionite. In addition, other reducing agents are contained, such as ascorbic acid, sodium formaldehyde sulfoxylate, sodium bisulfite or sodium dithionite. Because the polymerization reaction of the monomer is carried out in the presence of starch and starch also acts as a reducing agent, it is usually not necessary to use other reducing agents at the same time. The redox initiators are used, for example, in amounts of 0.05 to 10%, preferably 0.1 to 5%, based on the monomers.

The emulsion polymerization of monomers I and/or III is carried out in an aqueous medium in the presence of starch having a molar mass Mw of 1000 to 65000. The monomers can be polymerized by an emulsion polymerization process, carried out according to a feed schedule. Preferably, the degraded starch and an aqueous solution of a heavy metal salt are first added, and the monomers are added continuously or intermittently, alone or as a mixture, to the oxidatively active component of the redox initiator, preferably hydrogen peroxide.

The addition can be effected uniformly or non-uniformly during the metering, ie the metering rate can be varied.

The polymerization is usually carried out under nitrogen protection. During the polymerization, it should be ensured that the components are thoroughly mixed. Therefore, the reaction mixture is preferably stirred during the entire period of the polymerization and any subsequent post-polymerization.

The polymerization is usually carried out at a temperature of 30°C to 100°C, preferably 50°C to 110°C. Pressure reactors for continuous polymerization in kettle cascades or flow tubes.

To improve the dispersing effect, conventional ionic, nonionic or zwitterionic emulsifiers can be added to the polymerization batch. If appropriate, conventional emulsifiers are used only in an amount of 0-3%, preferably 0.02%-2%, based on the total amount of monomers used. Examples of conventional emulsifiers are reaction products of long-chain monohydric alcohols (C10-C22 alkanols) with 4-50 mol of ethylene oxide and/or propylene oxide per mole of alcohol, or ethoxylated phenols or alkoxylated alcohols esterified with sulfuric acid, which are usually used in a base-neutralized form. Other conventional emulsifiers are, for example, sodium alkanesulfonates, sodium alkyl sulfates, sodium dodecylbenzenesulfonate, sulfosuccinates, alkyl quaternary ammonium salts, alkyl benzyl ammonium salts (e.g. dimethyl C12-C18 alkyl benzyl ammonium chloride), primary, secondary or tertiary fatty amine salts, quaternary aminoamine compounds, alkyl pyridinium salts, alkyl oxazolium salts.

During the emulsion polymerization, the monomers can be metered directly into the initial mixture or can be added to the polymerization batch in the form of an aqueous emulsion or microemulsion. For this purpose, the monomers are emulsified in water using the abovementioned customary emulsifiers.

The polymerization is carried out at a pH of 2-9, preferably in a weakly acidic range of 3-5.5. The pH can be adjusted to a desired value before or during the polymerization using a conventional acid, such as hydrochloric acid, sulfuric acid or acetic acid, or using a base, such as sodium hydroxide solution, potassium hydroxide solution, ammonia, ammonium carbonate, etc. The dispersion is preferably adjusted to a pH of 5-7 using sodium hydroxide solution, potassium hydroxide solution or ammonia after the polymerization is completed.

In order to remove the remaining monomer as far as possible from the treatment agent, it is advantageous to carry out postpolymerization. For this reason, after the main polymerization ends, in the treatment agent, add an initiator selected from hydrogen peroxide, peroxide, hydroperoxide and/or azo, or a combination of initiator and a suitable reducing agent, such as ascorbic acid or sodium bisulfite. Preferably, an oil-soluble initiator that is insoluble in water is used, such as conventional organic peroxide, such as dibenzoyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumyl hydroperoxide or dicyclohexyl peroxydicarbonate.

For the post-polymerization, the reaction mixture is heated, for example, to a temperature corresponding to the temperature of the main polymerization or 20° C. higher, preferably 10° C. higher. The main polymerization is completed when the polymerization initiator has been consumed or the monomer conversion is, for example, at least 98%, preferably at least 99.5%. Tert-butyl peroxide is preferably used for the post-polymerization. The post-polymerization is carried out, for example, at 35° C. to 100° C., typically at 45° C. to 95° C.

After the polymerization is completed, a complexing agent for heavy metal ions may be added to the treating agent in an amount such that all heavy metal ions are bonded in a complexed manner.

The solid content of the treating agent containing the modified sugar substance is, for example, 5% to 50%, preferably 15% to 40%.

The above-mentioned treatment agents containing modified sugar substances are used as sizing materials for paper, paperboard and cardboard. They can be used as surface sizing materials and as machine sizing materials according to conventional dosages. They are preferably used as surface sizing materials. The treatment agents of the present application can be processed by all methods suitable for surface sizing. The treatment agent can be applied to the surface of the paper to be sizing by, for example, a sizing press, a film press or a gate roller coater. For application, the treatment agent is usually added to the sizing press liquid in an amount of 0.05-3% by weight based on solid matter, and depends on the desired sizing degree of the paper to be processed. In addition, the sizing press liquid can contain other substances, such as starch, pigment, brightener, increasing agent, fixing agent, antifoaming agent, retention agent. The amount of polymer applied to the surface of the paper product is, for example, 0.005-1.0/m ² , preferably 0.01-0.5g/m ² .

The above-mentioned treatment agent is used as a surface treatment agent for fiber fabrics and can be applied to the treated object by existing known methods. Usually, the treatment agent is diluted in water, and it is attached to the surface of the treated object by known methods such as dip coating, spray coating, and foaming cloth, and then dried. In addition, when necessary, it can be used together with a suitable cross-linking agent (such as blocked isocyanate) for vulcanization. Insect repellents, softeners, antibacterial agents, flame retardants, antistatic agents, wrinkle-proofing agents, etc. can also be added to the treatment agent of the present application for use together. The concentration of the polymer in the treatment solution in contact with the substrate can be 0.01%-10% (especially when dip coating), for example, 0.05-10% by weight.

2. Test Method

Paper product handling and testing methods

The paper products that can be processed include thin paper, thick paper, cardboard, or pulp molding, ranging from 300 grams per unit area ( ^m2 ) to 80 grams per unit area ( ^m2 ) of kraft paper, and from 200 grams per unit area (m2) to 100 grams per unit area ( ^m2 ) of kraft paper. It can process anything from 30g thin paper to 200g paper-plastic products per unit area ( ^m2 ).

The raw materials of paper products can be chemically bleached pulp or unbleached pulp, wood pulp, chemical mechanical pulp, mechanical pulp, etc. Resin components such as polyamide, polyolefin, polyvinyl alcohol, etc. may also be added to these pulp boards. The methods of paper product processing are as follows:

(1) Surface sizing treatment example:

Preparation of test paper: Paper product weight 50 g/ ^m2

Chemical pulp LBKP (broadleaf bleached kraft pulp) and NBKP (coniferous bleached kraft pulp) were used in a ratio of 5:5, and the pulp was debonded, and the debonding degree was 200 ml of Canadian freedom. In the papermaking process, cationic starch MC-2 type starch produced by Guangxi Mingyangyang Biochemical Company was added, and the added amount was 1% by weight of the pulp, and a fourdrinier paper machine was used to make thin paper with a weight of 50 g/ ^m2 .

The starch used for sizing is Y+L corn oxidized starch produced by Jiangxi Hongda Chemical Company, with a concentration of 5%. The starch solution is first heated to above 90°C for gelatinization. After gelatinization, the pH value of the sizing solution is tested to be 8.5-8.9, and then the treatment agent is added. The concentration of the treatment agent in the starch solution is 1%-15% by weight (the concentration of the entire treatment agent, not the solid concentration). The temperature of the starch solution is controlled to be not less than 70°C, and the paper product is first subjected to surface sizing treatment, with the liquid absorption exceeding 70%, and then dried to obtain the treated paper product.

(2) Surface coating example:

Preparation of test paper products: Paper product weight 230 g/ ^m2

The paper product is composed of five layers, of which the bottom and top layers are chemical pulp boards LBKP (bleached kraft pulp from broadleaf trees) plus NBKP (bleached kraft pulp from coniferous trees), with a ratio of 7:3. The middle three layers are made of chemical mechanical pulp or mechanical pulp boards, which are compounded on the paper machine into a cardboard with a weight of 230 g/ ^m2 .

The coating starch used is the coating starch AS-28 produced by Guangxi Mingyangyang Biochemical Company. The starch concentration is 20%. The starch is added with water and heated to above 90°C for gelatinization. After gelatinization, the pH value of the coating solution is tested to be 8.4-8.7. Then the treatment agent is added. The concentration of the treatment agent in the starch solution is 1%-15% (the concentration of the entire treatment agent, not the solid concentration). The starch temperature is controlled to be not less than 50°C, and the paper product coating machine is used to apply it to the top layer of the paperboard. The coating amount is 3-8 g/ ^m2 .

Oil and water repellency evaluation

Oil repellency evaluation

Hot oil resistance test

The treated paper products are made into containers that can hold liquids. Hot oil (salad oil, peanut oil or rapeseed oil) at 85°C is poured into the paper container. The container is observed for 20 minutes to see if there is any penetration, and rating and scoring are performed.

5 points: no surface discoloration;

4 points means the surface is slightly discolored;

3 points: surface discoloration and slight penetration;

2 points for severe penetration.

Water repellency evaluation

Cobb Test

The test is carried out according to GB/T1540-2002 or ISO 535:1991.

The principle is to measure the weight (g) of water absorbed by a 100 cm ² paper supporting 10 mm of water in 1 minute, and convert the value into weight per square meter (g/m ² ).

The Cobb absorbency tester usually uses a flip cylinder tester. The metal cylinder is a cylinder, and its inner cross-sectional area is generally (100±0.2) ^cm2 , and the corresponding inner diameter is (112.8±0.2)mm. If a small area cylinder is used, the recommended area should be no less than ^50cm2 . At this time, the volume of water should be reduced accordingly to ensure a water height of 10mm. The cylinder height is 50mm, and the part of the cylinder ring surface that contacts the sample should be smooth and have sufficient roundness to prevent the edge of the cylinder from damaging the sample. To prevent water leakage, a layer of elastic but non-absorbent rubber pad or gasket should be added to the flip-type cylinder cover and the flat pressing base. The width of the metal pressure roller should be (200±0.5)mm, the mass should be (10±0.5)kg, and the surface should be smooth.

Cut the treated paper product samples into 10 (125±5) mm square or ￠(125±5) mm circular specimens (5 on the front and 5 on the back). For instruments with small test areas, the specimen size should be slightly larger than the outer diameter of the cylinder to avoid leakage caused by too small specimens and to avoid affecting operation by too large specimens.

Before placing the sample, ensure that the cylinder ring surface and rubber pad in contact with the sample are dry, and do not touch the test area with your hands. Use a measuring cylinder to measure 100mL of water and pour it into the cylinder, then place the weighed sample on the cylinder ring surface with the test surface facing downward. Cover the sample with a gland and clamp it to fix it to the cylinder.

Turn the cylinder 180°, start the stopwatch and absorb water for 60 seconds. Turn the cylinder upright 10s to 15s before the end of water absorption, loosen the gland clamping device, and remove the sample. Note that the test water should be replaced after every 5 tests to avoid affecting the test results. At the moment when the specified water absorption time is reached, place the sample removed from the cylinder with the water absorption surface facing down on the pre-laid absorbent paper. Put another piece of absorbent paper on the sample, and then immediately use a metal roller to roll back and forth once within 4s without adding other pressure to absorb the remaining water on the surface of the sample. Take out the sample quickly, fold it in half with the water absorption surface inward, and then fold it in half again and weigh it, accurate to 0.001g. For thick cardboard, the sample may not be easy to fold, in which case the second weighing should be carried out as soon as possible.

The Cobb value is expressed by the following formula: C = (g2-g1)/F

Where: C-cobb value;

g2-weight of the sample after water absorption;

g1- weight of sample before water absorption;

F - ^100cm2 test area.

3. Examples and Comparative Examples

See Table 1 for chemical abbreviations:

Table 1 Codes and chemical formulas of various substances

Example 1

165 g of Mingyang Biochemical's cationic tapioca starch RS-118 (DS value = 0.045) was added to the flask. The flask was equipped with a stirrer and a device for detecting the internal temperature. 1100 g of deionized water were added while stirring, and the mixture was then heated to 85° C. and stirred for 30 minutes, after which 7.0 g of glacial acetic acid and 1.4 g of 10% ferrous sulfate heptahydrate were added. Then, 6.24 g of 18% hydrogen peroxide solution were metered in over 30 minutes.

Then, a feed of 300 g of deionized water, 0.26 g of a mixture of alkanesulfonates with an average chain length of C15 (40%), 1.5 g of dodecyl mercaptan, 210 g of Si-B3 monomer was started and metered in over 120 minutes. At the same time, 56.2 g of 18% strength hydrogen peroxide solution were added over 150 minutes.

The mixture was post-polymerized for 30 minutes and then cooled to 50° C. Then, 17.6 g of 10% tert-butyl hydroperoxide was added within 70 minutes, and finally 1.1 g of 40% ethylenediaminetetraacetic acid sodium salt aqueous solution was added, and the reaction mixture was cooled to 30° C. and adjusted with deionized water to obtain an emulsion with a solid content of 20%. The comparison between the theoretical solid content and the actual measured solid content showed that the monomer conversion rate was greater than 98%.

Take part of the emulsion obtained above and add anhydrous ethanol to break the emulsion. After standing for 24 hours, filter it. The solid obtained by filtration is placed in a drying oven at 70°C and dried to constant weight to obtain a crude product. Then use acetone as a solvent and extract it in a Soxhlet extractor for 8 hours to remove a small amount of polymer that is not chemically bonded to the starch, and then dry it. Take the dried sample and analyze it with infrared spectroscopy (FTIR). The results show that the silicone polymer is successfully connected to the starch through chemical bonds.

Embodiment 2-8

The same as Example 1, except that Si-B3 is replaced by monomers I with different structures as follows, namely Si-NB3 (Example 2), Si-ph-B3 (Example 3), Si-OCN-B3 (Example 4), Si-OCO-B3 (Example 5), Si-B2 (Example 6), Si-N2-B2 (Example 7), Si-5 (average molecular weight is 500) (Example 8).

Take part of the emulsion obtained above and add anhydrous ethanol to break the emulsion. After standing for 24 hours, filter it. The solid obtained by filtration is placed in a drying oven at 70°C and dried to constant weight to obtain a crude product. Then use acetone as a solvent and extract it in a Soxhlet extractor for 8 hours to remove a small amount of polymer that is not chemically bonded to the starch, and then dry it. Take the dried sample and analyze it with infrared spectroscopy (FTIR). The results show that the silicone polymer is successfully connected to the starch through chemical bonds.

Embodiment 9

165 grams of Mingyang Biochemical's cationic tapioca starch RS-118 (DS value = 0.045) were added to a flask equipped with a stirrer and a device for detecting the internal temperature. 1100 grams of deionized water were added while stirring, and the mixture was then heated to 85°C and stirred for 30 minutes, followed by the addition of 7.0 grams of glacial acetic acid and 1.4 grams of 10% ferrous sulfate heptahydrate. Then, 6.24 grams of 18% hydrogen peroxide solution were metered in over 30 minutes.

Then, a feed of 300 g of deionized water, 0.26 g of a mixture of alkanesulfonates with an average chain length of C15 (40%), 1.5 g of tert-dodecyl mercaptan, 210 g of Si-B3 monomer and 20 g of MAA monomer was started and metered in over 120 minutes. At the same time, 56.2 g of 18% strength hydrogen peroxide solution were added over 150 minutes.

The mixture was post-polymerized for 30 minutes and then cooled to 50° C. Then, 17.6 g of 10% tert-butyl hydroperoxide was added over 70 minutes, and finally 1.1 g of 40% ethylenediaminetetraacetic acid sodium salt aqueous solution was added, and the reaction mixture was cooled to 30° C. and adjusted with deionized water to obtain an emulsion with a solid content of 20%. Comparison of the theoretical solid content with the actual measured solid content showed that the monomer conversion rate was greater than 98%.

Take part of the emulsion obtained above and add anhydrous ethanol to break the emulsion. After standing for 24 hours, filter it. The solid obtained by filtration is placed in a drying oven at 70°C and dried to constant weight to obtain a crude product. Then use acetone as a solvent and extract it in a Soxhlet extractor for 8 hours to remove a small amount of polymer that is not chemically bonded to the starch, and then dry it. Take the dried sample and analyze it with infrared spectroscopy (FTIR). The results show that the silicone polymer is successfully connected to the starch through chemical bonds.

Performance Testing

The emulsion synthesized in the example was used as a treatment agent to test several articles:

1) Test of paper products: 50 g/ ^m2 thin paper was selected and treated by surface sizing. The starch used for sizing was Y+L corn oxidized starch produced by Jiangxi Hongda Chemical Company, and the pH value of the sizing solution was measured to be 8.7. The concentrations of the treatment agent were 5wt%, 4wt%, and 3wt%, respectively, and the heat oil resistance and Cobb water absorption value were tested. The specific test results are shown in Table 2.

2) Test of paper products: 230 g/ ^m2 cardboard was selected and treated by coating. The coating starch used was the AS-28 produced by Guangxi Mingyang Biochemical Company, and the pH value of the coating liquid was tested to be 8.5. The concentrations of the treatment agent were 5wt%, 4wt%, and 3wt%, respectively, and the heat oil resistance and Cobb water absorption value were tested. The specific test results are shown in Table 2.

Table 2 Test performance comparison table

It can be seen from Table 2 that, under alkaline conditions, the treatment agents obtained in Examples 1-9 all showed good oil and water repellency after being used to treat paper products by surface sizing or coating. It can be seen from the data of Example 8 that the treatment agent containing the structural unit generated by the silicon monomer I-A has a better oil repellency effect than the treatment agent containing the structural unit generated by the silicon monomer I-B.

Comparative Example 1

Into a four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer and a stirrer, 75 g of Si-B3, 40 g of DN, 20 g of HEMA and 135 g of methyl ethyl ketone (hereinafter referred to as MEK) were added, nitrogen was passed through for 30 minutes, the temperature was slowly raised to 60°C, 1.4 g of peroxide initiator tert-butyl peroxypivalate was added, the reaction temperature was controlled at 60°C for 20 hours, and about 270 g of a polymer solution was obtained with a solid content of about 50%.

525 g of water and 15 g of glacial acetic acid were added, and the mixture was stirred at 60° C. for more than 1 hour. MEK in the solution was distilled off under reduced pressure to obtain an aqueous dispersion with a solid content of 20%.

Comparative Examples 2-8

Exactly the same as Comparative Example 1, except that Si-B3 is replaced by the following monomers I with different structures, namely Si-NB3 (Comparative Example 2), Si-ph-B3 (Comparative Example 3), Si-OCN-B3 (Comparative Example 4), Si-OCO-B3 (Comparative Example 5), Si-B2 (Comparative Example 6), Si-N2-B2 (Comparative Example 7), Si-5 (average molecular weight is 500) (Comparative Example 8).

Comparative Example 9

The same method as in Example 1, except that Si-B3 was replaced by vinyltriisopropoxysilane, did not result in a stable dispersion but a non-flowable gel.

The comparative example was tested using the same test method as in Examples 1-9, and the test results are shown in Table 3.

Table 3 Comparative test performance table

It can be seen from Table 3 that, under alkaline conditions, the aqueous dispersions obtained from Comparative Examples 1-8 cannot impart good water and oil repellency to paper products by surface sizing or coating.

Comparative Example 9 is to use other alkoxysilane monomers for polymerization in the presence of starch. Since the structure is easily hydrolyzed and then condensed, the polymer is cross-linked into a gel, and a stable aqueous dispersion cannot be obtained.

The technical solution of the present application is not limited to the above-mentioned specific embodiments, and all technical variations made according to the technical solution of the present application fall within the protection scope of the present application.

Claims (14)

A modified carbohydrate substance, comprising a carbohydrate substance and an organosilicon polymer, wherein the carbohydrate substance and the organosilicon polymer are connected by chemical bonds, and the organosilicon polymer comprises a structural unit produced by a monomer I, wherein the general structural formula of the monomer I is shown in Formula I: M-Z or Z-M-Z Formula I Wherein, M contains a polymerizable functional group; Z is selected from the following structures,
In Z, R ₃ is each independently selected from a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₀ aryl group, a C ₇ -C ₁₂ aralkyl group, a C ₇ -C ₁₂ alkaryl group, a C ₁ -C ₂₀ alkoxy group or an R ₄ -OR ₅ - group, R ₄ is a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₀ aryl group, a C ₇ -C ₁₂ aralkyl group or a C ₇ -C ₁₂ alkaryl group, R ₅ is a C ₁ -C ₂₀ alkylene group, and 1≤a≤200; _Y1 and _Y2 are the same or different, and are independently selected from _C1 - _C20 alkyl, _C6 - _C20 aryl, _C7 - _C12 aralkyl, _C7 - _C12 alkaryl or the following structure (1):
_R7 is each independently selected from a _C1 - _C20 alkyl group, a _C6 - _C20 aryl group, a _C7 - _C12 aralkyl group or a _C7 - _C12 alkaryl group; _R8 is each independently selected from a _C1 - _C20 alkyl group, _{a C6} - _C20 aryl group, a _C7 - _C12 aralkyl group, a _C7 - _C12 alkaryl group, a _C1 - _C20 alkoxy group or an _R9 - _OR10- group, wherein _R9 is a _C1 - _C20 alkyl group, a _C6 - _C20 aryl group, a _C7 - _C12 aralkyl group or a _C7 - _C12 alkaryl group, _{and R10} is a _C1 - _C20 alkylene group, and 0≤b≤200. The modified carbohydrate substance according to claim 1, characterized in that: M is shown in formula I-1: _CH2 ＝C( _R1 )-XB- I-1 In formula I-1, _R1 is selected from a hydrogen atom or a _C1 - _C20 alkyl group; B is selected from a _C1 - _C20 alkylene group, a _C6 - _C20 arylene group, and a combination thereof; X is selected from the group represented by X-1 and X-2, -C(O)-O X-1 -C(O)-N(R ₂ ) X-2 R ₂ is selected from a hydrogen atom or a C ₁ -C ₂₀ alkyl group; and/or M is shown in formula I-2: _CH2 ＝C( _R1 )-WB- I-2 In formula I-2, R ₁ is selected from a hydrogen atom or a C ₁ -C ₂₀ alkyl group; W is selected from the group represented by W-1, W-2, W-3 and W-4,
-OC(O)-N(R ₂ )- W-2 -O-C(O)-O-       W-3 -OC(O)-ODN(R ₂ )- W-4 _R2 is selected from a hydrogen atom or a _C1 - _C20 alkyl group, and D is a _C1 - _C20 alkylene group; when W is selected from W-1, B is absent or is a C1- _C20 alkylene group; when W is selected from W-2, W-3, and W- _{4, B is selected from a C1-C20 alkylene group} , a _C6 - _C20 arylene group, and a combination thereof; and/or M is shown in formula I-3:
In formula I-3, R ₁ is selected from a hydrogen atom or a C ₁ -C ₂₀ alkyl group, and B is independently selected from a C ₁ -C ₂₀ alkylene group, a C ₆ -C ₂₀ arylene group, and a combination thereof. The modified carbohydrate substance according to claim 1 or 2 is characterized in that: the organosilicon polymer also includes a structural unit produced by monomer III, monomer III is a monomer having an anion supplying group and a polymerizable unsaturated group, and the anion supplying group is a carboxyl group or a sulfonic acid group. The modified carbohydrate substance according to any one of claims 1 to 3, characterized in that the mass content of the structural unit produced by monomer I in the organosilicon polymer is 5%-100%, preferably 30%-75%, more preferably 40%-60%; and/or The mass content of the saccharide substance in the modified saccharide substance is 5%-90%, preferably 20%-70%, more preferably 30%-60%; and/or The mass content of the structural unit produced by monomer III in the organosilicon polymer is 0.5%-30%, preferably 3%-20%, more preferably 5%-15%. The modified carbohydrate substance according to any one of claims 1 to 4, characterized in that the carbohydrate substance is selected from one or more of starch substances, cellulose substances, galactomannan substances, xanthan gum substances, alginate substances, pectin substances, chitosan substances, gum arabic substances, carrageenan substances, agar substances and gellan gum substances; Preferably, the carbohydrate material is selected from starch materials, and the starch material is selected from one or more of starch, modified starch, degraded starch and modified degraded starch, preferably selected from one or more of cationic modified starch, anionic modified starch and nonionic modified starch; And/or the weight average molecular weight of the carbohydrate substance is 1000-65000. The modified carbohydrate substance according to any one of claims 1 to 5, characterized in that: Monomer I includes silicon monomer I-A and/or silicon monomer I-B; The general formula of the silicon monomer IA is the same as that of formula I, and also satisfies the following conditions: when a is 1, _Y1 and/or _Y2 are structures of formula (1); when a is greater than 1 and ≤ 200, at least one _Y1 is a structure of formula (1) and/or at least one _Y2 is a structure of formula (1); The general formula of silicon monomer IB is the same as formula I, and also satisfies that _Y1 and _Y2 are the same or different, and are independently selected from _C1 - _C20 alkyl, _C6 - _C20 aryl, _C7 - _C12 aralkyl and _C7 - _C12 alkaryl. The modified sugar substance according to any one of claims 1 to 6, characterized in that: In formula I-1, R ₁ is selected from a hydrogen atom or a C ₁ -C ₁₀ alkyl group, preferably R ₁ is selected from a hydrogen atom or a methyl group; B is a C ₁ -C ₁₀ alkylene group, preferably B is a C ₁ -C ₆ alkylene group; in X, R ₂ is selected from a hydrogen atom or a C ₁ -C ₁₀ alkyl group, preferably R ₂ is selected from a hydrogen atom or a methyl group; In formula I-2, R ₁ is selected from a hydrogen atom or a C ₁ -C ₁₀ alkyl group, preferably R ₁ and R ₂ are selected from a hydrogen atom or a methyl group, B and D are C ₁ -C ₁₀ alkylene groups, preferably B and D are C ₁ -C ₆ alkylene groups; In formula I-3, R ₁ is selected from a hydrogen atom or a C ₁ -C ₁₀ alkyl group, preferably R ₁ is selected from a hydrogen atom or a methyl group; B is a C ₁ -C ₁₀ alkylene group; In Z, _R3 is independently _C1 - _C10 alkyl, _C6 - _C10 aryl, C7- _C12 aralkyl, _C7 - _C12 alkaryl, _C1 - _C10 alkoxy or _R4 - _OR5 -group, _R4 is _C1 - _C10 alkyl, _C6 - _C10 aryl, _C7 - _C12 aralkyl or _C7 - _C12 alkaryl, _R5 is _C1 - _C10 alkylene, 1≤a≤100; _R7 is independently _C1 - _C10 alkyl, C6- _C10 aryl, _C7 - _C12 aralkyl or _C7 - _C12 alkaryl; _R8 is independently _C1 -C10 alkyl, _{C6 - C10 aryl} , _C7 - _C12 R 9 is a C 1 -C ₁₂ aralkyl group, a C ₇ -C ₁₂ alkaryl group, a C ₁ -C ₁₀ alkoxy group or a R ₉ -OR ₁₀ - group, wherein R ₉ is a C ₁ -C ₁₀ alkyl group, a C ₆ -C ₁₀ aryl group, a C ₇ -C ₁₂ aralkyl group or a C ₇ -C ₁₂ alkaryl group, R ₁₀ is a C ₁ -C ₁₀ alkylene group, and 0≤b≤100. The modified carbohydrate substance according to any one of claims 1 to 7, characterized in that Z is selected from the following structures: Z is independently selected from one or more of the following structures i-1 to i-6:

Z is preferred from

One or more of; R is each independently selected from a C ₁ -C ₁₀ alkyl group, a C ₆ -C ₁₀ aryl group, a C ₇ -C ₁₂ aralkyl group or a C ₇ -C ₁₂ alkaryl group; Me represents methyl, ph represents phenyl; 1≤m+1≤60, preferably 1≤m+1≤30; 0≤p≤60, preferably 0≤p≤30; 0≤q≤60, preferably 0≤q≤30; 1≤x≤9, preferably 1≤x≤7, and each x may be the same or different. The modified sugar substance according to any one of claims 1 to 8, characterized in that: Silicon monomer I-A is selected from CH ₂ =C(CH ₃ )C(O)-O-(CH ₂ ) ₃ Si(OSi(CH ₃ ) ₃ ) ₃ ; CH ₂ =CHC(O)-O-(CH ₂ ) ₃ Si(OSi(CH ₃ ) ₃ ) ₃ ; CH ₂ =C(CH ₃ )C(O)-O-(CH ₂ ) ₃ Si(CH ₃ )(OSi(CH ₃ ) ₃ ) ₂ ; CH ₂ =CHC(O)-O-(CH ₂ ) ₃ Si(CH ₃ )(OSi(CH ₃ ) ₃ ) ₂ ; CH ₂ =C(CH ₃ )C(O)-NH-(CH ₂ ) ₃ Si(OSi(CH ₃ ) ₃ ) ₃ ; CH ₂ =CHC(O)-NH-(CH ₂ ) ₃ Si(OSi(CH ₃ ) ₃ ) ₃ ; CH ₂ =C(CH ₃ )C(O)-NH-(CH ₂ ) ₃ Si(CH ₃ )(OSi(CH ₃ ) ₃ ) ₂ ; CH ₂ =CHC(O)-NH-(CH ₂ ) ₃ Si(CH ₃ )(OSi(CH ₃ ) ₃ ) ₂ ; CH ₂ =C(CH ₃ )C(O)-O-(CH ₂ ) ₃ Si(OSi(CH ₂ CH ₃ ) ₃ ) ₃ ; CH ₂ =CHC(O)-O-(CH ₂ ) ₃ Si(OSi(CH ₂ CH ₃ ) ₃ ) ₃ ; CH ₂ =C(CH ₃ )C(O)-O-CH ₂ -Si(OSi(CH ₃ ) ₃ ) ₃ ; CH ₂ =C(CH ₃ )C(O)-O-(CH ₂ ) ₃ Si(CH ₃ )[O-[Si(CH ₃ ) ₂ O]n-Si(CH ₃ ) ₂ C ₄ H ₉ ] ₂ , 0≤n≤25; CH ₂ =CH-ph-Si(OSi(CH ₃ ) ₃ ) ₃ (ph means ); CH ₂ =CH-ph-(CH ₂ ) ₂ Si(OSi(CH ₃ ) ₃ ) ₃ (ph means ); CH ₂ =CH-OC(O)-NH-(CH ₂ ) ₃ Si(OSi(CH ₃ ) ₃ ) ₃ ; CH ₂ =CH-OC(O)-O-(CH ₂ ) ₃ -Si(OSi(CH ₃ ) ₃ ) ₃ ; CH ₂ =CH-OC(O)-O-(CH ₂ ) ₂ -NH-(CH ₂ ) ₃ Si(OSi(CH ₃ ) ₃ ) ₃ ; CH ₂ =CH-C(O)-N[-(CH ₂ ) ₃ -Si(OSi(CH ₃ ) ₃ ) ₃ ] ₂ ; CH ₂ =CH-C(O)-N[-(CH ₂ ) ₃ -Si(CH ₃ )(OSi(CH ₃ ) ₃ ) ₂ ] ₂ ; and/or Silicon monomer I-B is selected from CH ₂ =C(CH ₃ )C(O)-O-(CH ₂ ) ₃ [Si(CH ₃ ) ₂ O]n-Si(CH ₃ ) ₂ C ₄ H ₉ (C ₄ H ₉ represents a butyl group), 1≤n≤25; CH ₂ =C(CH ₃ )C(O)-O-(CH ₂ ) ₃ [Si(CH ₃ ) ₂ O]n-Si(CH ₃ ) ₂ C ₈ H ₁₇ , 1≤n≤25; CH ₂ =C(CH ₃ )C(O)-O-(CH ₂ ) ₃ [Si(CH ₃ ) ₂ O]n-Si(CH ₃ ) ₃ , 1≤n≤25; CH ₂ ＝CH-ph-(CH ₂ ) ₃ [Si(CH ₃ ) ₂ O]n-Si(CH ₃ ) ₂ C ₄ H ₉ (C ₄ H ₉ represents a butyl group, ph represents ), 1≤n≤25; CH ₂ ＝CH-OC(O)-NH-(CH ₂ ) ₃ -[Si(CH ₃ ) ₂ O]n-Si(CH ₃ ) ₂ C ₄ H ₉ (C ₄ H ₉ represents a butyl group), 1≤n≤ 25; CH ₂ ＝CH-OC(O)-O-(CH ₂ ) ₃ -[Si(CH ₃ ) ₂ O]n-Si(CH ₃ ) ₂ C ₄ H ₉ (C ₄ H ₉ represents a butyl group), 1≤n≤25; CH ₂ ＝CH-OC(O)-O-(CH ₂ ) ₂ -NH-(CH ₂ ) ₃ [Si(CH ₃ ) ₂ O]n-Si(CH ₃ ) ₂ C ₄ H ₉ (C ₄ H ₉ represents a butyl group), 1≤n≤25; CH ₂ ＝CH—C(O)—N[—(CH ₂ ) ₃ —(Si(CH ₃ ) ₂ O) _n —Si(CH ₃ ) ₂ C ₄ H ₉ ] ₂ (C ₄ H ₉ represents a butyl group), 1≤n≤25; CH ₂ =C(CH ₃ )-C(O)-N[-(CH ₂ ) ₃ -(Si(CH ₃ ) ₂ O) _n -Si(CH ₃ ) ₂ C ₄ H ₉ ] ₂ (C ₄ H ₉ represents a butyl group), 1≤n≤25; and/or Monomer III is selected from (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, 2-acrylamide-2-methylpropanesulfonic acid, vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, vinylbenzenesulfonic acid, acrylamide-tert-butylsulfonic acid or salts thereof. A treatment agent comprising the modified sugar substance according to any one of claims 1 to 9, an optional emulsifier and an aqueous medium, preferably, the aqueous medium comprises water and an optional organic solvent. A method for preparing the treating agent according to claim 10, comprising subjecting the monomer to a polymerization reaction in the presence of a saccharide substance and an initiator, preferably comprising the following steps: (1) mixing a sugar substance and water to obtain a first mixture; (2) Adding monomers, initiators, optional organic solvents, optional emulsifiers and optional molecular weight regulators to the first mixture to carry out polymerization reaction. Use of the modified sugar substance according to any one of claims 1 to 9, the treating agent according to claim 10, or the treating agent prepared by the method according to claim 11 in paper products, fiber fabrics, leather, non-woven fabrics, asbestos, fur, concrete, stone or plastic. A water- and oil-repellent product, comprising a product and the modified sugar substance according to any one of claims 1 to 9 or the treating agent according to claim 10 or the treating agent prepared by the method according to claim 11, wherein the product is paper products, fiber fabrics, leather, non-woven fabrics, asbestos, fur, concrete, stone or plastic. Preferably, the modified sugar substance according to any one of claims 1 to 9, the treating agent according to claim 10, or the treating agent prepared by the method according to claim 11 is attached to the surface and/or the inside of the product. A method for treating a product, comprising contacting the product with the modified sugar substance described in any one of claims 1 to 9, the treating agent described in claim 10, or the treating agent prepared by the method described in claim 11, wherein the product is a paper product, a fiber fabric, leather, a non-woven fabric, asbestos, fur, concrete, stone or plastic. Preferably, the contact is achieved by an internal treatment process, a surface sizing process, a surface coating process or an immersion treatment process.